Multi -component formulations of organometallic reagents

Abstract

Provided are stable multi-component formulations of organometallic reagents showing long-term stability, high reactivity, non-pyrophoricity, and low viscosity at room temperature. Said formulations are particularly suitable as reagents in synthesis having a good compatibility with liquid handlers and flow reactors, allowing an easy reaction work-up and product isolation, and offering an improved or at least similar reactivity compared to conventional organometallic reagents. Further provided is a facile and scalable preparation method of said stable multi-component formulations and the use thereof as reagents in chemical synthesis.

Description

MULTI -COMPONENT FORMULATIONS OF ORGANOMETALLIC REAGENTSField of Invention

[0001] The present application claims the benefit of priority of U.S. provisional patent application no. 63 / 651,547 filed on May 24, 2024, the content of which is hereby incorporated in its entirety.

[0002] The present invention provides stable multi-component formulations of organometallic reagents. Said formulations are characterized by long-term stability, high reactivity, non-pyrophoricity, and low viscosity at room temperature. They are particularly suitable as reagents in synthesis having a good compatibility with liquid handlers and flow reactors, allowing an easy reaction work-up and product isolation, and offering an improved or at least similar reactivity compared to conventional organometallic reagents. The present invention further relates to facile and scalable preparation methods of said stable multi-component formulations and to the use of said multi-component formulations as reagents in chemical synthesis.

[0003] The multi-component formulations were subjected to extensive stability, reactivity, pyrophoricity and viscosity tests to demonstrate increased stability and reactivity, non-pyrophoricity and low viscosity properties. Further, the formulations were used as reagents in chemical synthesis to demonstrate easier handling and improved or at least similar reactivity compared to conventional pyrophoric organometallic reagents.Background

[0004] Organometallic reagents are compounds characterized by the presence of at least one chemical bond between a carbon atom forming part of an organic moiety and a metal / metalloid element.[1]Such reagents play a crucial role in contemporary chemical synthesis. Among them, organolithium, zinc, magnesium, and aluminum reagents are most commonly used.[2]'[7]Notably, most of these reagents are pyrophoric and could ignite spontaneously in contact with air / moisture. Particularly, alkyllithium reagents display a highly reactive behavior, posing significant safety risks. Due to these reasons, often alternative reagents are preferred despite the desirable reactivity of organolithiums. This is particularly the case with tert-butyllithium.[8]

[0005] The pyrophoric characteristics of these reagents can be attributed to two primary factors: (1) exothermic behavior during acid-base reactions, and (2) the ignition of the commonly used dispersing solvent. A critical review of these small chain hydrocarbon solvents reveals that these solvents contribute heavily to the increased pyrophoricity, and hazards associated with these reagents due to their (1) low heat capacity, (2) low flash points, and (3) high volatility. Recent realization of these concerns has driven chemists to develop alternative solvent systems and create new generation nonpyrophoric versions of these extremely useful organometallic reagents.[9]

[0006] In addressing these issues, recent works have followed three different routes, which include (1) the organogel approach,[9](2) the deep eutectic solvent systems,

[0010] ,

[0011] and (3) the use of oligomeric hydrocarbons.

[0012] ,

[0013] Most of these demonstrations are performed with organolithium reagents considering their extensive range of application in chemical synthesis and their pyrophoricity.

[0007] Conceptually, the first approach employs organogelators, which are selfassembling, gel-forming materials when in contact with organic solvents.Incorporation of an organolithium reagent into a gel could result in solid-like handling characteristics, potentially protecting the reactive species from air and moisture, thereby providing stabilization and easier handling.

[0008] This concept was demonstrated for phenyl and n-butyllithium by Smith and coworkers.[9]This report remains only as a proof of concept as these organolithium gels suffered substantially from (1) gel instability upon long-term storage, (2) tedious synthetic procedures and severe scalability concerns, (3) higher loadings of organogelators (up to 18 wt%), to obtain a solid form, and (4) a limited scope of organolithiums.

[0009] Deep eutectic solvents are a class of ionic liquids distinguished by their ability to form eutectic mixtures consisting of two or three components. Typically, these mixtures comprise Lewis or Brpnsted acids and bases, encompassing a diverse range of anionic and / or cationic species. Hevia and coworkers reported that DESs could act as a reaction medium to facilitate a range of reactions with organolithiums,minimizing their hydrolysis and other side reactions under open-air conditions.

[0011]

[0010] Further, Capriati and coworkers reported the application of the NaCI / HiO eutectic system to enable sp2-sp3couplings with moderate yields.

[0010] Apart from these reaction-based demonstrations, there is no report highlighting the storage of organolithiums using these solvents. It is quite predictable that, with the available DESs, the substantial decomposition of organolithiums is expected.

[0011] In the last case, the application of hydrocarbon oligomers as an alternative solvent for organolithiums gained popularity since the initial reports from the Bergbreiter group.

[0012]

[0013] These studies primarily employed poly(a-olefins) as the dispersing medium. It is important to note that PAOs are non-volatile, non-toxic, and have poor oxygen solubility. These reports describe non-pyrophoric solutions of organolithium and other organometallic reagents.

[0012] US 2021 / 0178375 Al relates to a solution including an oligomeric hydrocarbon such as poly(a-olefin) and a reactive organometallic reagent, wherein the poly(a-olefin) (PAO) is said to be a safer alternative to pentane, cyclohexane, hexanes, and heptanes as solvents for highly reactive organometallic compounds like alkyllithium reagents.

[0013] Despite the above-mentioned results, the widespread adoption of this technology remained limited. Primarily due to (1) the extreme viscosity of these solutions: Their viscosity ranged well above 10 CSt at 100°C, which poses substantial difficulty in handling these materials for reactions, especially for batch reactors, flowreactors, and liquid handlers. (2) Non-scalable synthetic procedures: These procedures often require the purification of PAOs with other polar solvents and the complete removal of hexane or pentane from the mixtures, which poses a substantial safety risk for the operations in scale. (3) Long-term storage concerns of these organolithium solutions, the studies indicated that considerable molarity drop of reagents over 60 minutes (up to 30% for tert-butyllithium, and 20% for n-butyllithium), pointing to the instability of these solutions.

[0014] For these reasons, there is a continuous need to develop improved multicomponent formulations of organometallic reagents and preparation methods thereofwhich overcome the disadvantages from the prior art.

[0015] In particular, there is a need for improved multi-component formulations of organometallic reagents which show long-term stability, high reactivity, nonpyrophoricity and low viscosity at room temperature, which are particularly suitable as reagents in synthesis having good compatibility with liquid handlers and flow reactors, allowing an easy reaction work-up and product isolation, and offering improved or at least similar reactivity compared to conventional organometallic reagents. Moreover, there is a need to develop facile and scalable preparation methods for said improved multi-component formulations.Objective

[0016] The present invention aims to overcome the disadvantages known from the prior art.

[0017] Hence, it is an objective of the present invention to provide a formulation comprising an organometallic reagent, wherein said formulation shows long-term stability, high reactivity, non-pyrophoricity and low viscosity at room temperature.

[0018] It is a further objective of the present invention to provide a formulation comprising an organometallic reagent, wherein said formulation is particularly suitable as reagent in synthesis, has good compatibility with liquid handlers and flow reactors, allows an easy reaction work-up and product isolation, and offers improved or at least similar reactivity compared to conventional organometallic reagents.

[0019] Yet another object of the present invention is to provide a facile and scalable preparation method for said formulations comprising organometallic reagents showing the aforementioned beneficial effects.Summary

[0020] The embodiments of the present invention described hereinafter provide a technical solution to the aforementioned objectives.

[0021] In a first embodiment, the present invention provides a formulationcomprising:(a) an organometallic compound;(b) a first solvent, which is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 or more carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 or more carbon atoms or alkynes having 8 or more carbon atoms;(c) a second solvent, which is one or more selected from aliphatic or aromatic hydrocarbons having 7 or less carbon atoms; and(d) an additive selected from the list consisting of tertiary amines, tertiary phosphines, ethers and sulfides; characterized in that the additive is present in a stoichiometric or sub-stoichiometric amount with respect to the organometallic compound.

[0022] In a second embodiment, the present invention provides a method for preparing a formulation according to the first embodiment, which method comprises mixing (a), (b), (c) and (d) in any order, wherein (a) is an organometallic compound; (b) is a first solvent, which is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 or more carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 or more carbon atoms or alkynes having 8 or more carbon atoms; (c) is a second solvent, which is one or more selected from aliphatic or aromatic hydrocarbons having 7 or less carbon atoms; and (d) is an additive selected from the list consisting of tertiary amines, tertiary phosphines, ethers and sulfides; characterized in that the additive is present in a stoichiometric or sub-stoichiometric amount with respect to the organometallic compound.

[0023] In a third embodiment, the present invention relates to the use of a formulation according to the first embodiment as a reagent in chemical synthesis.

[0024] The present invention is further described in the embodiments followinghereinafter in the detailed description.Brief Description of the Figures

[0025] None.Detailed DescriptionFormulation

[0026] In a first embodiment, the present invention provides a formulation comprising:(a) an organometallic compound;(b) a first solvent, which is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 or more carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 or more carbon atoms or alkynes having 8 or more carbon atoms;(c) a second solvent, which is one or more selected from aliphatic or aromatic hydrocarbons having 7 or less carbon atoms; and(d) an additive selected from the list consisting of tertiary amines, tertiary phosphines, ethers and sulfides; characterized in that the additive is present in a stoichiometric or sub-stoichiometric amount with respect to the organometallic compound.

[0027] The formulations as described herein have several advantageous properties that position them as leading-edge reagents for next-generation organometallic reagents. The advantageous properties include long-term stability, high reactivity, non-pyrophoricity, low viscosity at room temperature, good compatibility with liquid handlers and flow reactors, easy reaction work-up and product isolation, and improved or at least similar reactivity compared to conventional organometallic reagents. Moreover, the formulations can be produced by facile and scalable methods starting from commercially available, concentrated solutions of organometallic swithout the necessity for solvent removal, which is a mandatory and arduous procedure in the methods described in the prior art.

[0028] Preferably, the organometallic compound is selected from the list consisting of organolithium compounds, organomagnesium compounds, organoaluminum compounds, and organozinc compounds.

[0029] It is preferred that the organometallic compound comprises one or more saturated or unsaturated aliphatic moieties, saturated or unsaturated alicyclic moieties, aromatic moieties, hetero aromatic moieties or combinations thereof, which optionally comprise independently from each other one or more substituents selected from the list consisting of -F, -Cl, -Br, -CN, -CF3, -C6F5, -OCH3, -OCF3, -OC6H5, -OCH2C6H5, -N(CH3)2, -N[Si(CH3)3]2, -Si(CH3)3, -Si(CF3)3, 1,3-dioxolan, and 1,3-dioxan, and wherein the hetero aromatic moieties comprise independently from each other one or more heteroatoms selected from N, O, and S, preferably S.

[0030] It is more preferred that the organometallic compound comprises one or more saturated aliphatic moieties having 1 to 30 carbon atoms, unsaturated aliphatic moieties having 2 to 30 carbon atoms, saturated alicyclic moieties having 3 to 30 carbon atoms, unsaturated alicyclic moieties having 3 to 30 carbon atoms, aromatic moieties having 6 to 30 carbon atoms, heteroaromatic moieties having 2 to 29 carbon atoms, or combinations thereof, which optionally comprise independently from each other one or more substituents selected from the list consisting of -F, -Cl, -Br, -CN, -CF3, -C6F5, -OCH3, -OCF3, -OC6H5, -OCH2C6H5, -N(CH3)2, -N[Si(CH3)3]2, -Si(CH3)3, -Si(CF3)3, 1,3-dioxolan, and 1,3-dioxan, and wherein the heteroaromatic moieties comprise independently from each other one or more heteroatoms selected from N, O, and S, preferably S.

[0031] It is even more preferred that the organometallic compound comprises one or more saturated aliphatic moieties having 1 to 20 carbon atoms, unsaturated aliphatic moieties having 2 to 20 carbon atoms, saturated alicyclic moieties having 3 to 20 carbon atoms, unsaturated alicyclic moieties having 3 to 20 carbon atoms, aromatic moieties having 6 to 22 carbon atoms, heteroaromatic moieties having 2 to 21 carbon atoms, or combinations thereof, which optionally comprise independently from each other one or more substituents selected from the list consisting of -F, -Cl,-Br, -CN, -CF3, -C6F5, -OCH3, -OCF3, -OC6H5, -OCH2C6H5, -N(CH3)2, -N[Si(CH3)3]2, -Si(CH3)3, -Si(CF3)3, 1,3-dioxolan, and 1,3-dioxan, and wherein the heteroaromatic moieties comprise independently from each other one or more heteroatoms selected from N, O, and S, preferably S.

[0032] It is still even more preferred that the organometallic compound comprises one or more saturated aliphatic moieties having 1 to 10 carbon atoms, unsaturated aliphatic moieties having 2 to 10 carbon atoms, saturated alicyclic moieties having 3 to 10 carbon atoms, unsaturated alicyclic moieties having 3 to 10 carbon atoms, aromatic moieties having 6 to 14 carbon atoms, heteroaromatic moieties having 3 to 13 carbon atoms, or combinations thereof, which optionally comprise independently from each other one or more substituents selected from the list consisting of -F, -Cl, -Br, -CN, -CF3, -C6F5, -OCH3, -OCF3, -OC6H5, -OCH2C6H5, -N(CH3)2, -N[Si(CH3)3]2, -Si(CH3)3, -Si(CF3)3, 1,3-dioxolan, and 1,3-dioxan, and wherein the heteroaromatic moieties comprise independently from each other one or more heteroatoms selected from N, O, and S, preferably S.

[0033] It is most preferred that the organometallic compound comprises one or more saturated aliphatic moieties having 1 to 6 carbon atoms, unsaturated aliphatic moieties having 2 to 6 carbon atoms, saturated alicyclic moieties having 3 to 6 carbon atoms, unsaturated alicyclic moieties having 3 to 6 carbon atoms, aromatic moieties having 6 to 10 carbon atoms, heteroaromatic moieties having 4 to 9 carbon atoms, or combinations thereof, which optionally comprise independently from each other one or more substituents selected from the list consisting of -F, -Cl, -Br, -CN, -CF3, -CeFs, -OCH3, -OCF3, -OC6H5, -OCH2C6H5, -N(CH3)2, -N[Si(CH3)3]2, -Si(CH3)3, -Si(CF3)3, 1,3-dioxolan, and 1,3-dioxan, and wherein the heteroaromatic moieties comprise independently from each other one or more heteroatoms selected from N, O, and S, preferably S.

[0034] In some embodiments, the organometallic compound is optionally present as an alkali metal halide salt complex, preferably as an alkali metal fluoride salt complex, alkali metal chloride salt complex, alkali metal bromide salt complex, or alkali metal iodide salt complex, more preferably as an alkali metal chloride salt complex or alkali metal bromide salt complex, most preferably as a LiCl complex or LiBr complex. This particularly applies to organomagnesium compounds,organoaluminum compounds, and organozinc compounds.

[0035] Preferred organolithium compounds are selected from the list consisting of methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec- butyllithium, isobutyllithium, tert-butyllithium, n-hexyllithium, (trimethylsilyl)methyllithium, and phenyllithium.

[0036] Preferred organomagnesium compounds are selected from the list consisting of methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium chloride, n- propylmagnesium bromide, isopropylmagnesium chloride, isopropylmagnesium bromide, cyclopropylmagnesium chloride, cyclopropylmagnesium bromide, n- butylmagnesium chloride, n-butylmagncsium bromide, .sec-butylmagncsium chloride, sec-butylmagnesium bromide, isobutylmagnesium chloride, isobutylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, n- pentylmagnesium chloride, n-pcntyl magnesium bromide, 1,1- dimethylpropylmagnesium chloride, cyclopentylmagnesium chloride, cyclopentylmagnesium bromide, 2,2-dimethylpropylmagnesium chloride, 2,2- dimethylpropylmagnesium bromide, hexylmagnesium chloride, hexylmagnesium bromide, cyclohexylmagnesium chloride, cyclohexylmagnesium bromide, heptylmagnesium chloride, heptylmagnesium bromide, octylmagnesium chloride, octylmagnesium bromide, (2-ethylhexyl)magnesium chloride, (2- ethylhexyl)magnesium bromide, nonylmagnesium chloride, nonylmagnesium bromide, decylmagnesium chloride, decylmagnesium bromide, 3,7- dimethyloctylmagnesium chloride, 3,7-dimethyloctylmagnesium bromide, dodecylmagnesium chloride, dodecylmagnesium bromide, tetradecylmagnesium chloride, tetradecylmagnesium bromide, pentadecylmagnesium chloride, pentadecylmagnesium bromide, octadecylmagnesium chloride, octadecylmagnesium bromide, (cyclohexylmethyl)magnesium chloride, (cyclohexylmethyl)magnesium bromide, phenethylmagnesium chloride, phenethylmagnesium bromide, (trimethylsilyl)methylmagnesium chloride, (trimethylsilyl)methylmagnesium bromide, 2-methyl-2-phenylpropylmagnesium chloride, 2-methyl-2- phenylpropylmagnesium bromide, benzylmagnesium chloride, benzylmagnesium bromide, 3-methylbenzylmagnesium chloride, 3-methylbenzylmagnesium bromide, 4-methylbenzylmagnesium chloride, 4-methylbenzylmagnesium bromide, 2- methoxybenzylmagnesium chloride, 2-methoxybenzylmagnesium bromide, 3- methoxybenzylmagnesium chloride, 3-methoxybenzylmagnesium bromide, 4- methoxybenzylmagnesium chloride, 4-methoxybenzylmagnesium bromide, 4- fluorobenzylmagnesium chloride, 4-fluorobenzylmagnesium bromide, 2- bromobenzylmagnesium chloride, 2-bromobenzylmagnesium bromide, 3- bromobenzylmagnesium chloride, 3-bromobenzylmagnesium bromide, (1,3-dioxolan- 2-ylmethyl)magnesium bromide, (l,3-dioxan-2-ylethyl)magnesium bromide, vinylmagnesium chloride, vinylmagnesium bromide, ethynylmagnesium chloride, ethynylmagnesium bromide, allylmagnesium chloride, allylmagnesium bromide, 2- methylallylmagnesium chloride, 2-methylallylmagnesium bromide, isopropenylmagnesium chloride, isopropenylmagnesium bromide, 1- propynylmagnesium chloride, 1-propynylmagnesium bromide, 1 -methyl- 1- propenylmagnesium chloride, 1 -methyl- 1 -propenylmagnesium bromide, l-methyl-2- propenylmagnesium chloride, l-methyl-2-propenylmagnesium bromide, 2-methyl-l- propenylmagnesium chloride, 2-methyl-l -propenylmagnesium bromide, 3- butenylmangnesium chloride, 3-butenylmangnesium bromide, 4-pentenylmagnesium chloride, 4-pentenylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, pentafluorophenylmagnesium bromide, p- tolylmagnesium chloride, -tolylmagncsium bromide, o-tolylmagnesium chloride, o- tolylmagnesium bromide, 2,3-dimethylphenylmagnesium bromide, 2,5- dimethylphenylmagnesium bromide, 2,6-dimethylphenylmagnesium bromide (= 2- mesitylmagnesium bromide), 3,5-dimethylphenylmagnesium bromide, 3,5- bis(trifluoromethyl)phenylmagnesium bromide, 4-isopropylphenylmagnesium bromide, 2,4,6-triisopropylphenylmagnesium bromide, 4-tert-butylphenylmagnesium bromide, 2-methoxyphenylmagnesium bromide, 3-methoxyphenylmagnesium bromide, 4-methoxyphenylmagnesium bromide, 4- (trifluoromethoxy)phenylmagnesium bromide, 4-methoxy-2-methylphenylmagnesium bromide, 2,4-dimethoxyphenylmagnesium bromide, 3,4-dimethoxyphenylmagnesium bromide, 3,5-dimethoxyphenylmagnesium chloride, 3,5-dimethoxyphenylmagnesium bromide, 3,4,5-trimethoxyphenylmagnesium bromide, 4-phenoxyphenylmagnesium bromide, 3-fluorophenylmagnesium bromide, 4-fluorophenylmagnesium bromide, 4- fluoro-2-methylphenylmagnesium bromide, 3,4-difluorophenylmagnesium bromide, 3,5-difluorophenylmagnesium bromide, 3-chlorophenylmagnesium bromide, 4-chlorophenylmagnesium bromide, 3,4-dichlorophenylmagnesium bromide, 3,5- dichlorophenylmagnesium bromide, 3-chloro-4-fluorophenylmagnesium bromide, 4- chloro-3-fluorophenylmagnesium bromide, 2-benzyloxyphenylmagnesium bromide, 4-benzyloxyphenylmagnesium bromide, (4- / V, / V-dimcthyl) aniline magnesium bromide, 3-[bis(trimethylsilyl)amino)phenylmagnesium chloride, 3- [bis(trimethylsilyl)amino)phenylmagnesium bromide, 4- [bis(trimethylsilyl)amino]phenylmagnesium chloride, 4- [bis(trimethylsilyl)amino]phenylmagnesium bromide, 1 -naphthylmagnesium bromide,2-naphthylmagnesium bromide, 2-biphenylmagnesium bromide, 4- biphenylmagnesium bromide, 9-phenanthrylmagnesium bromide, 3-methyl-2- thienylmagnesium bromide, 2-thienylmagnesium bromide, 3 -thienylmagnesium iodide, di-n-butylmagnesium, divinylmagnesium, diphenylmagnesium, and LiCl complexes and LiBr complexes thereof.

[0037] Preferred organoaluminum compounds are selected from the list consisting of trimethylaluminum, triisobutylaluminum, methylaluminoxane, triethylaluminum, bis(trimethylaluminum)- 1 ,4-diazabicyclo[2.2.2]octane adduct, diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, diethylaluminum chloride, diethylaluminum cyanide, triphenylaluminum, diethylaluminum ethoxide, diisobutylaluminum chloride, lithium diisobutyl-tert-butoxyaluminum hydride, diisobutyl aluminum hydride, and LiCl complexes and LiBr complexes thereof.

[0038] Preferred organozinc compounds are selected from the list consisting of dimethylzinc, diethylzinc, diisopropyl zinc, diphenylzinc, bis(pentafluorophenyl)zinc, 1 -propylzinc bromide, 2-propylzinc bromide, cyclobutylzinc bromide, cyclohexylzinc bromide, 4-cyanobutylzinc bromide, (l,3-dioxolan-2-ylmethyl)zinc bromide, phenethylzinc bromide, phenylzinc iodide, bis(pentafluorophenyl)zinc, benzylzinc bromide, methylzinc chloride, isobutylzinc bromide, 3-ethoxy-3-oxopropylzinc bromide, 1-adamantylzinc bromide, 4-methylbenzylzinc chloride, 2-(l,3-dioxolan-2- yl)]ethyl]zinc bromide, 2-thienylzinc bromide, 3, 5 -difluorobenzylzinc bromide, 4- methoxybenzylzinc chloride, 4-fluorobenzylzinc chloride, 2-adamantylzinc bromide,3-butenylzinc bromide, 3 -cyanopropylzinc bromide, a-methylbenzylzinc bromide, 6- ethoxy-6-oxohexylzinc bromide, 3 -chlorobenzylzinc chloride, 2-fluorobenzylzinc chloride, 4-chlorobenzylzinc chloride, phenethylzinc bromide, 2,6-difluorophenylzincbromide, 2-thiazolylzinc bromide, 2-ethylbutylzinc bromide, 6-methyl-2-pyridylzinc bromide, 5-ethoxy-5-oxopentylzinc bromide, 4-methyl-2-pyridylzinc bromide, (2- chloro-5-pyridyl)methylzinc chloride, 3-methoxybenzylzinc chloride, .sec-butylzinc bromide, 5-ethoxycarbonyl-2-fufurylzinc chloride, 2-cyanobenzylzinc bromide, 2- (ethoxycarbonyl)phenylzinc bromide, 4-bromo-2-fluorophenylzinc iodide, 4-[(4- morpholino)methyl]phenylzinc iodide, 2,5-difluoro-4-methoxyphenylzinc bromide, 4- cyanobenzylzinc bromide, 3 -methoxyphenylzinc iodide, 2, 3, 4,5,6- pentafluorobenzylzinc bromide, 5-bromo-2-methoxybenzylzinc chloride, 2- fluorophenylzinc iodide, 3-acetoxyphenylzinc iodide, 2,5-dichlorophenylzinc iodide, 4-acetoxyphenylzinc iodide, 2,6-difluorobenzylzinc bromide, 3-chloro-4- methylphenylzinc iodide, 4-ethoxybenzylzinc chloride, 2,6-dichlorobenzylzinc chloride, 2-pyridylzinc bromide, (2-naphthylmethyl)zinc bromide, and LiCl complexes and LiBr complexes thereof.

[0039] In a preferred embodiment of the present invention, the organometallic compound is selected from the list consisting of(1) methyllithium, ethyllithium, n -propyllithium, isopropyllithium, n-butyl lithium, sec-butyllithium, isobutyllithium, tert-butyllithium, n -hexyllithium, (trimethylsilyl)methyllithium, and phenyllithium;(2) methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium chloride, n-propylmagnesium bromide, isopropylmagnesium chloride, isopropylmagnesium bromide, cyclopropylmagnesium chloride, cyclopropylmagnesium bromide, n-butylmagncsium chloride, n-butylmagncsium bromide, sec-butylmagnesium chloride, .sec-butylmagncsium bromide, isobutylmagnesium chloride, isobutylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, n-pcntylmagncsium chloride, n- pentylmagnesium bromide, 1,1 -dimethylpropylmagnesium chloride, cyclopentylmagnesium chloride, cyclopentylmagnesium bromide, 2,2- dimethylpropylmagnesium chloride, 2,2-dimethylpropylmagnesium bromide, hexylmagnesium chloride, hexylmagnesium bromide, cyclohexylmagnesium chloride, cyclohexylmagnesium bromide, heptylmagnesium chloride, heptylmagnesium bromide, octylmagnesium chloride, octylmagnesium bromide, (2-ethylhexyl)magnesium chloride, (2-ethylhexyl)magnesium bromide, nonylmagnesium chloride, nonylmagnesium bromide, decylmagnesium chloride, decylmagnesium bromide, 3,7-dimethyloctylmagnesium chloride, 3,7-dimethyloctylmagnesium bromide, dodecylmagnesium chloride, dodecylmagnesium bromide, tetradecylmagnesium chloride, tetradecylmagnesium bromide, pentadecylmagnesium chloride, pentadecylmagnesium bromide, octadecylmagnesium chloride, octadecylmagnesium bromide, (cyclohexylmethyl)magnesium chloride, (cyclohexylmethyl)magnesium bromide, phenethylmagnesium chloride, phenethylmagnesium bromide, (trimethylsilyl)methylmagnesium chloride, (trimethylsilyl)methylmagnesium bromide, 2-methyl-2-phenylpropylmagnesium chloride, 2-methyl-2-phenylpropylmagnesium bromide, benzylmagnesium chloride, benzylmagnesium bromide, 3-methylbenzylmagnesium chloride, 3- methylbenzylmagnesium bromide, 4-methylbenzylmagnesium chloride, 4- methylbenzylmagnesium bromide, 2-methoxybenzylmagnesium chloride, 2- methoxybenzylmagnesium bromide, 3-methoxybenzylmagnesium chloride, 3- methoxybenzylmagnesium bromide, 4-methoxybenzylmagnesium chloride, 4- methoxybenzylmagnesium bromide, 4-fluorobenzylmagnesium chloride, 4- fluorobenzylmagnesium bromide, 2-bromobenzylmagnesium chloride, 2- bromobenzylmagnesium bromide, 3-bromobenzylmagnesium chloride, 3- bromobenzylmagnesium bromide, (l,3-dioxolan-2-ylmethyl)magnesium bromide, (l,3-dioxan-2-ylethyl)magnesium bromide, vinylmagnesium chloride, vinylmagnesium bromide, ethynylmagnesium chloride, ethynylmagnesium bromide, allylmagnesium chloride, allylmagnesium bromide, 2-methylallylmagnesium chloride, 2-methylallylmagnesium bromide, isopropenylmagnesium chloride, isopropenylmagnesium bromide, 1-propynylmagnesium chloride, 1- propynylmagnesium bromide, 1 -methyl- 1 -propenylmagnesium chloride, 1 -methyl- 1- propenylmagnesium bromide, l-methyl-2-propenylmagnesium chloride, l-methyl-2- propenylmagnesium bromide, 2-methyl-l -propenylmagnesium chloride, 2-methyl-l- propenylmagnesium bromide, 3-butenylmangnesium chloride, 3-butenylmangnesium bromide, 4-pentenylmagnesium chloride, 4-pentenylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, pentafluorophenylmagnesium bromide, -tolylmagncsium chloride, -tolylmagncsium bromide, o-tolylmagnesium chloride, o-tolylmagnesium bromide, 2,3- dimethylphenylmagnesium bromide, 2,5-dimethylphenylmagnesium bromide, 2,6-dimethylphenylmagnesium bromide (= 2-mesitylmagnesium bromide), 3,5- dimethylphenylmagnesium bromide, 3,5-bis(trifluoromethyl)phenylmagnesium bromide, 4-isopropylphenylmagnesium bromide, 2,4,6-triisopropylphenylmagnesium bromide, 4-tert-butylphenylmagnesium bromide, 2-methoxyphenylmagnesium bromide, 3-methoxyphenylmagnesium bromide, 4-methoxyphenylmagnesium bromide, 4-(trifluoromethoxy)phenylmagnesium bromide, 4-methoxy-2- methylphenylmagnesium bromide, 2,4-dimethoxyphenylmagnesium bromide, 3,4- dimethoxyphenylmagnesium bromide, 3,5-dimethoxyphenylmagnesium chloride, 3,5- dimethoxyphenylmagnesium bromide, 3,4,5-trimethoxyphenylmagnesium bromide, 4-phenoxyphenylmagnesium bromide, 3-fluorophenylmagnesium bromide, 4- fluorophenylmagnesium bromide, 4-fluoro-2-methylphenylmagnesium bromide, 3,4- difluorophenylmagnesium bromide, 3,5-difluorophenylmagnesium bromide, 3- chlorophenylmagnesium bromide, 4-chlorophenylmagnesium bromide, 3,4- dichlorophenylmagnesium bromide, 3,5-dichlorophenylmagnesium bromide, 3- chloro-4-fluorophenylmagnesium bromide, 4-chloro-3-fluorophenylmagnesium bromide, 2-benzyloxyphenylmagnesium bromide, 4-benzyloxyphenylmagnesium bromide, (4- / V-dimcthyl)anilinc magnesium bromide, 3- [bis(trimethylsilyl)amino)phenylmagnesium chloride, 3- [bis(trimethylsilyl)amino)phenylmagnesium bromide, 4- [bis(trimethylsilyl)amino]phenylmagnesium chloride, 4- [bis(trimethylsilyl)amino]phenylmagnesium bromide, 1 -naphthylmagnesium bromide, 2-naphthylmagnesium bromide, 2-biphenylmagnesium bromide, 4- biphenylmagnesium bromide, 9-phenanthrylmagnesium bromide, 3-methyl-2- thienylmagnesium bromide, 2-thienylmagnesium bromide, 3 -thienylmagnesium iodide, di-n-butylmagnesium, divinylmagnesium, diphenylmagnesium, and LiCl complexes and LiBr complexes thereof;(3) trimethylaluminum, triisobutylaluminum, methylaluminoxane, triethylaluminum, bis(trimethylaluminum)- 1 ,4-diazabicyclo[2.2.2]octane adduct, diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, diethylaluminum chloride, diethylaluminum cyanide, triphenylaluminum, diethylaluminum ethoxide, diisobutylaluminum chloride, lithium diisobutyl-tert-butoxyaluminum hydride,diisobutyl aluminum hydride, and LiCl complexes and LiBr complexes thereof; and(4) dimethylzinc, diethylzinc, diisopropyl zinc, diphenylzinc, bis(pentafluorophenyl)zinc, 1 -propylzinc bromide, 2-propylzinc bromide, cyclobutylzinc bromide, cyclohexylzinc bromide, 4-cyanobutylzinc bromide, (1,3- dioxolan-2-ylmethyl)zinc bromide, phenethylzinc bromide, phenylzinc iodide, bis(pentafluorophenyl)zinc, benzylzinc bromide, methylzinc chloride, isobutylzinc bromide, 3-ethoxy-3-oxopropylzinc bromide, 1-adamantylzinc bromide, 4- methylbenzylzinc chloride, 2-(l,3-dioxolan-2-yl)]ethyl]zinc bromide, 2-thienylzinc bromide, 3, 5 -difluorobenzylzinc bromide, 4-methoxybenzylzinc chloride, 4- fluorobenzylzinc chloride, 2-adamantylzinc bromide, 3-butenylzinc bromide, 3- cyanopropylzinc bromide, a-methylbenzylzinc bromide, 6-ethoxy-6-oxohexylzinc bromide, 3-chlorobenzylzinc chloride, 2-fluorobenzylzinc chloride, 4- chlorobenzylzinc chloride, phenethylzinc bromide, 2,6-difluorophenylzinc bromide, 2-thiazolylzinc bromide, 2-ethylbutylzinc bromide, 6-methyl-2-pyridylzinc bromide, 5-ethoxy-5-oxopentylzinc bromide, 4-methyl-2-pyridylzinc bromide, (2-chloro-5- pyridyl)methylzinc chloride, 3-methoxybenzylzinc chloride, .sec-butylzinc bromide, 5-ethoxycarbonyl-2-fufurylzinc chloride, 2-cyanobenzylzinc bromide, 2- (ethoxycarbonyl)phenylzinc bromide, 4-bromo-2-fluorophenylzinc iodide, 4-[(4- morpholino)methyl]phenylzinc iodide, 2,5-difluoro-4-methoxyphenylzinc bromide, 4- cyanobenzylzinc bromide, 3 -methoxyphenylzinc iodide, 2, 3, 4,5,6- pentafluorobenzylzinc bromide, 5-bromo-2-methoxybenzylzinc chloride, 2- fluorophenylzinc iodide, 3-acetoxyphenylzinc iodide, 2,5-dichlorophenylzinc iodide, 4-acetoxyphenylzinc iodide, 2,6-difluorobenzylzinc bromide, 3-chloro-4- methylphenylzinc iodide, 4-ethoxybenzylzinc chloride, 2,6-dichlorobenzylzinc chloride, 2-pyridylzinc bromide, (2-naphthylmethyl)zinc bromide, and LiCl complexes and LiBr complexes thereof.

[0040] In a more preferred embodiment of the present invention, the organometallic compound is selected from the list consisting of methyllithium, ethyllithium, n- propyllithium, isopropyllithium, n -butyllithium, .sec-butyllithium, isobutyllithium, tert-butyllithium, n -hexyllithium, (trimethylsilyl)methyllithium, phenyllithium, trimethylaluminum, and diethylzinc.

[0041] The first solvent is one or more selected from monomeric linear chain,branched chain or cyclic hydrocarbons having 8 or more carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 or more carbon atoms or alkynes having 8 or more carbon atoms. The oligomeric hydrocarbons are obtained through an olefin polymerization reaction of alkenes and alkynes, resulting in a linear chain backbone with attached side chains. Typical representatives include so-called poly(a-olefins).

[0042] Preferably, the first solvent is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 to 20 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 to 20 carbon atoms or alkynes having 8 to 20 carbon atoms.

[0043] More preferably, the first solvent is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 to 16 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 20 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 to 16 carbon atoms or alkynes having 8 to 16 carbon atoms.

[0044] Still more preferably, the first solvent is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 9 to 16 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 10 repeating units, which in each occurrence are independently from each other derived from alkenes having 9 to 12 carbon atoms or alkynes having 9 to 12 carbon atoms.

[0045] Most preferably, the first solvent is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 9 to 12 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 10 repeating units, which in each occurrence are independently from each other derived from alkenes having 9 to 12 carbon atoms or alkynes having 9 to 12 carbon atoms.

[0046] Still most preferably, the first solvent is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 10 to 16 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 10 repeating units, which in each occurrence are independently from each other derived from alkeneshaving 9 to 12 carbon atoms or alkynes having 9 to 12 carbon atoms.

[0047] In a preferred embodiment of the present invention, the first solvent is one or more selected from the list consisting of octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, and oligomeric poly(a-olefins) having from 2 to 6 repeating units, which in each occurrence are independently from each other derived from alkenes having 9 to 12 carbon atoms or alkynes having 9 to 12 carbon atoms.

[0048] In a more preferred embodiment of the present invention, the first solvent is one or more selected from the list consisting of octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, and oligomeric poly(a-olefins) having from 2 to 6 repeating units, wherein said oligomeric poly(a- olefins) are optionally hydrogenated and selected from poly(l -decene), poly(l- undecene), poly(l -dodecene), poly(l-decene-co-l-octene), poly(l-decene-co-l- octene-co- 1 -dodecene), poly( 1 -dodecene-co- 1 -octene), poly( 1 -dodecene-co- 1 - decene), PAO283, PAO287, PAO432, and PAO687.

[0049] In a most preferred embodiment of the present invention, the first solvent is one or more selected from the list consisting of decanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, and oligomeric poly(a-olefins) having from 2 to 6 repeating units, wherein said oligomeric poly(a-olefins) are optionally hydrogenated and selected from poly(l -decene), poly(l-decene-co-l-octene-co-l- dodecene), and poly(l-dodecene-co-l-decene).

[0050] As a first solvent, for example, SpectraSyn™ 4 (Exxon Mobile) can be used, which includes the following compounds: hydrogenated poly(l -decene) [CAS: 68037-01-4], hydrogenated poly(l-decene-co-l-octene-co-l-dodecene) [CAS: 163149-28-8], and hydrogenated poly(l -dodecene-co- 1 -decene) [CAS: 151006-60-9].

[0051] It is preferred that the oligomeric poly(a-olefins) have molecular weight in the range from 200 to 1,200 g / mol, preferably from 220 to 1,050 g / mol, more preferably from 280 to 1,010 g / mol.

[0052] Preferably, the second solvent is one or more selected from aliphatic linear chain, branched chain or cyclic hydrocarbons having 5 to 7 carbon atoms or aromatichydrocarbons having 6 or 7 carbon atoms.

[0053] Preferably, the second solvent is one selected from aliphatic linear chain, branched chain or cyclic hydrocarbons having 5 to 7 carbon atoms or aromatic hydrocarbons having 6 or 7 carbon atoms.

[0054] More preferably, the second solvent is one or more selected from the list consisting of n-pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n- hexane, 2-methylpentane, 3-methylpentane, 2,2, -dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3 -methylhexane, 2,2, -dimethylpentane, 2,3- dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpetane, 3-ethylpentane, 2,2,3- trimethylbutane, cycloheptane, benzene, and toluene.

[0055] More preferably, the second solvent is one selected from the list consisting of / -pcntanc, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, 2- methylpentane, 3-methylpentane, 2,2, -dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3 -methylhexane, 2,2, -dimethylpentane, 2,3- dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpetane, 3-ethylpentane, 2,2,3- trimethylbutane, cycloheptane, benzene, and toluene.

[0056] Preferably, the additive is selected from tertiary amine compounds having 3 to 30 carbon atoms, tertiary phosphine compounds having 3 to 30 carbon atoms, ether compounds having 4 to 30 carbon atoms, and sulfide compounds having 2 to 30 carbon atoms.

[0057] More preferably, the additive is selected from tertiary amine compounds having 3 to 24 carbon atoms, tertiary phosphine compounds having 3 to 24 carbon atoms, ether compounds having 2 to 20 carbon atoms, and sulfide compounds having 2 to 20 carbon atoms.

[0058] Most preferably, the additive is selected from tertiary amine compounds having 3 to 15 carbon atoms, tertiary phosphine compounds having 3 to 15 carbon atoms, ether compounds having 4 to 10 carbon atoms, and sulfide compounds having 4 to 10 carbon atoms.

[0059] It is preferred that the additive comprises one or more groups selected fromalkyl groups, aromatic groups, or protecting groups. Preferred protecting groups include benzyl and tosylate.

[0060] It is more preferred that the additive is selected from the list consisting ofN,N,N’ ,N’ -tetramethylethylenediamine (TMEDA), N,N,N’ ,N’ ’ ,N” -pentamethyl- diethylenetriamine (PMDTA), tri-tert-butylphosphine, di-tert-butyl ether, and di-tert- butyl sulfide.

[0061] Preferably, the molar ratio of the additive to the organometallic compound in the formulation is in the range from 0.0000001: 1 (100 ppb) to 1:1, preferably fromO.01:1 to 1:1, even preferably from 0.1:1 to 0.9:1, more preferably from to 0.3:1 to 0.7:1, even more preferably from 0.4:1 to 0.6:1, and most preferably about 0.1:1 or about 0.5:1.

[0062] Preferably, the volume ratio of the first solvent to the second solvent in the formulation is in the range from 50:50 to 99:1, preferably from 50:50 to 95:5, more preferably from 65:35 to 90:10, even more preferably from 75:25 to 85:15, and most preferably about 80:20.

[0063] Preferably, the concentration of the organometallic compound in the formulation is in the range from 0.01 mol / L to 12 mol / L, preferably from 0.1 mol / L to 6.0 mol / L, more preferably from 0.2 mol / L to 5.0 mol / L, even more preferably from 0.5 to 4.0 mol / L, and most preferably from 0.5 mol / L to 3.0 mol / L.

[0064] More preferably, the molar ratio of the additive to the organometallic compound in the formulation is in the range from 0.0000001:1 (100 ppb) to 1:1, preferably from 0.01:1 to 1:1, even preferably from 0.1:1 to 0.9:1, more preferably from to 0.3:1 to 0.7:1, even more preferably from 0.4:1 to 0.6:1, and most preferably about 0.1:1 or about 0.5:1; and the volume ratio of the first solvent to the second solvent in the formulation is in the range from 50:50 to 99:1, preferably from 50:50 to 95:5, more preferably from 65:35 to 90:10, even more preferably from 75:25 to 85:15, and most preferably about 80:20.

[0065] More preferably, the molar ratio of the additive to the organometallic compound in the formulation is in the range from 0.0000001:1 (100 ppb) to 1:1, preferably from 0.01:1 to 1:1, even preferably from 0.1:1 to 0.9:1, more preferablyfrom to 0.3:1 to 0.7:1, even more preferably from 0.4:1 to 0.6:1, and most preferably about 0.1:1 or about 0.5:1; and the concentration of the organometallic compound in the formulation is in the range from 0.01 mol / L to 12 mol / L, preferably from 0.1 mol / L to 6.0 mol / L, more preferably from 0.2 mol / L to 5.0 mol / L, even more preferably from 0.5 to 4.0 mol / L, and most preferably from 0.5 mol / L to 3.0 mol / L.

[0066] More preferably, the volume ratio of the first solvent to the second solvent in the formulation is in the range from 50:50 to 99:1, preferably from 50:50 to 95:5, more preferably from 65:35 to 90:10, even more preferably from 75:25 to 85:15, and most preferably about 80:20; and the concentration of the organometallic compound in the formulation is in the range from 0.01 mol / L to 12 mol / L, preferably from 0.1 mol / L to 6.0 mol / L, more preferably from 0.2 mol / L to 5.0 mol / L, even more preferably from 0.5 to 4.0 mol / L, and most preferably from 0.5 mol / L to 3.0 mol / L.

[0067] Most preferably, the molar ratio of the additive to the organometallic compound in the formulation is in the range from 0.0000001:1 (100 ppb) to 1:1, preferably from 0.01:1 to 1:1, even preferably from 0.1:1 to 0.9:1, more preferably from to 0.3:1 to 0.7:1, even more preferably from 0.4:1 to 0.6:1, and most preferably about 0.1:1 or about 0.5:1; the volume ratio of the first solvent to the second solvent in the formulation is in the range from 50:50 to 99:1, preferably from 50:50 to 95:5, more preferably from 65:35 to 90:10, even more preferably from 75:25 to 85:15, and most preferably about 80:20; and the concentration of the organometallic compound in the formulation is in the range from 0.01 mol / L to 12 mol / L, preferably from 0.1 mol / L to 6.0 mol / L, more preferably from 0.2 mol / L to 5.0 mol / L, even more preferably from 0.5 to 4.0 mol / L, and most preferably from 0.5 mol / L to 3.0 mol / L.

[0068] It is preferred in the present invention that the organometallic compound is selected from the list consisting of organolithium compounds, organomagnesium compounds, organoaluminum compounds, and organozinc compounds; that the first solvent is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 to 20 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 to 20 carbon atoms or alkynes having 8 to 20 carbon atoms; that the second solvent is one or more selected from aliphatic linear chain, branched chain or cyclic hydrocarbons having 5 to 7 carbon atoms or aromatichydrocarbons having 6 or 7 carbon atoms; and that the additive is selected from tertiary amine compounds having 3 to 30 carbon atoms, tertiary phosphine compounds having 3 to 30 carbon atoms, ether compounds having 4 to 30 carbon atoms, and sulfide compounds having 2 to 30 carbon atoms.

[0069] It is more preferred in the present invention that the organometallic compound is selected from the list consisting of(1) methyllithium, ethyllithium, n-propyl lithium, isopropyllithium, n -butyl lithium, sec-butyllithium, isobutyllithium, tert-butyllithium, n-hcxyllithium, (trimethylsilyl)methyllithium, phenyllithium;(2) methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium chloride, n-propylmagnesium bromide, isopropylmagnesium chloride, isopropylmagnesium bromide, cyclopropylmagnesium chloride, cyclopropylmagnesium bromide, n-butylmagncsium chloride, n-butylmagncsium bromide, sec-butylmagnesium chloride, .sec-butylmagncsium bromide, isobutylmagnesium chloride, isobutylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, n-pcntylmagncsium chloride, n- pentylmagnesium bromide, 1,1 -dimethylpropylmagnesium chloride, cyclopentylmagnesium chloride, cyclopentylmagnesium bromide, 2,2- dimethylpropylmagnesium chloride, 2,2-dimethylpropylmagnesium bromide, hexylmagnesium chloride, hexylmagnesium bromide, cyclohexylmagnesium chloride, cyclohexylmagnesium bromide, heptylmagnesium chloride, heptylmagnesium bromide, octylmagnesium chloride, octylmagnesium bromide, (2- ethylhexyl)magnesium chloride, (2-ethylhexyl)magnesium bromide, nonylmagnesium chloride, nonylmagnesium bromide, decylmagnesium chloride, decylmagnesium bromide, 3,7-dimethyloctylmagnesium chloride, 3,7-dimethyloctylmagnesium bromide, dodecylmagnesium chloride, dodecylmagnesium bromide, tetradecylmagnesium chloride, tetradecylmagnesium bromide, pentadecylmagnesium chloride, pentadecylmagnesium bromide, octadecylmagnesium chloride, octadecylmagnesium bromide, (cyclohexylmethyl)magnesium chloride, (cyclohexylmethyl)magnesium bromide, phenethylmagnesium chloride, phenethylmagnesium bromide, (trimethylsilyl)methylmagnesium chloride,(trimethylsilyl)methylmagnesium bromide, 2-methyl-2-phenylpropylmagnesium chloride, 2-methyl-2-phenylpropylmagnesium bromide, benzylmagnesium chloride, benzylmagnesium bromide, 3-methylbenzylmagnesium chloride, 3- methylbenzylmagnesium bromide, 4-methylbenzylmagnesium chloride, 4- methylbenzylmagnesium bromide, 2-methoxybenzylmagnesium chloride, 2- methoxybenzylmagnesium bromide, 3-methoxybenzylmagnesium chloride, 3- methoxybenzylmagnesium bromide, 4-methoxybenzylmagnesium chloride, 4- methoxybenzylmagnesium bromide, 4-fluorobenzylmagnesium chloride, 4- fluorobenzylmagnesium bromide, 2-bromobenzylmagnesium chloride, 2- bromobenzylmagnesium bromide, 3-bromobenzylmagnesium chloride, 3- bromobenzylmagnesium bromide, (l,3-dioxolan-2-ylmethyl)magnesium bromide, (l,3-dioxan-2-ylethyl)magnesium bromide, vinylmagnesium chloride, vinylmagnesium bromide, ethynylmagnesium chloride, ethynylmagnesium bromide, allylmagnesium chloride, allylmagnesium bromide, 2-methylallylmagnesium chloride, 2-methylallylmagnesium bromide, isopropenylmagnesium chloride, isopropenylmagnesium bromide, 1-propynylmagnesium chloride, 1- propynylmagnesium bromide, 1 -methyl- 1 -propenylmagnesium chloride, 1 -methyl- 1- propenylmagnesium bromide, l-methyl-2-propenylmagnesium chloride, l-methyl-2- propenylmagnesium bromide, 2-methyl-l -propenylmagnesium chloride, 2-methyl-l- propenylmagnesium bromide, 3-butenylmangnesium chloride, 3-butenylmangnesium bromide, 4-pentenylmagnesium chloride, 4-pentenylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, pentafluorophenylmagnesium bromide, -tolylmagncsium chloride, -tolylmagncsium bromide, o-tolylmagnesium chloride, o-tolylmagnesium bromide, 2,3- dimethylphenylmagnesium bromide, 2,5-dimethylphenylmagnesium bromide, 2,6- dimethylphenylmagnesium bromide (= 2-mesitylmagnesium bromide), 3,5- dimethylphenylmagnesium bromide, 3,5-bis(trifluoromethyl)phenylmagnesium bromide, 4-isopropylphenylmagnesium bromide, 2,4,6-triisopropylphenylmagnesium bromide, 4-tert-butylphenylmagnesium bromide, 2-methoxyphenylmagnesium bromide, 3-methoxyphenylmagnesium bromide, 4-methoxyphenylmagnesium bromide, 4-(trifluoromethoxy)phenylmagnesium bromide, 4-methoxy-2- methylphenylmagnesium bromide, 2,4-dimethoxyphenylmagnesium bromide, 3,4- dimethoxyphenylmagnesium bromide, 3,5-dimethoxyphenylmagnesium chloride, 3,5- dimethoxyphenylmagnesium bromide, 3,4,5-trimethoxyphenylmagnesium bromide,4-phenoxyphenylmagnesium bromide, 3-fluorophenylmagnesium bromide, 4- fluorophenylmagnesium bromide, 4-fluoro-2-methylphenylmagnesium bromide, 3,4- difluorophenylmagnesium bromide, 3,5-difluorophenylmagnesium bromide, 3- chlorophenylmagnesium bromide, 4-chlorophenylmagnesium bromide, 3,4- dichlorophenylmagnesium bromide, 3,5-dichlorophenylmagnesium bromide, 3- chloro-4-fluorophenylmagnesium bromide, 4-chloro-3-fluorophenylmagnesium bromide, 2-benzyloxyphenylmagnesium bromide, 4-benzyloxyphenylmagnesium bromide, (4- / V-di methyl) aniline magnesium bromide, 3- [bis(trimethylsilyl)amino)phenylmagnesium chloride, 3- [bis(trimethylsilyl)amino)phenylmagnesium bromide, 4- [bis(trimethylsilyl)amino]phenylmagnesium chloride, 4- [bis(trimethylsilyl)amino]phenylmagnesium bromide, 1 -naphthylmagnesium bromide, 2-naphthylmagnesium bromide, 2-biphenylmagnesium bromide, 4- biphenylmagnesium bromide, 9-phenanthrylmagnesium bromide, 3-methyl-2- thienylmagnesium bromide, 2-thienylmagnesium bromide, 3 -thienylmagnesium iodide, di-n-butylmagnesium, divinylmagnesium, diphenylmagnesium, and LiCl complexes and LiBr complexes thereof;(3) trimethylaluminum, triisobutylaluminum, methylaluminoxane, triethylaluminum, bis(trimethylaluminum)- 1 ,4-diazabicyclo[2.2.2]octane adduct, diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, diethylaluminum chloride, diethylaluminum cyanide, triphenylaluminum, diethylaluminum ethoxide, diisobutylaluminum chloride, lithium diisobutyl-tert-butoxyaluminum hydride, diisobutyl aluminum hydride, and LiCl complexes and LiBr complexes thereof; and(4) dimethylzinc, diethylzinc, diisopropyl zinc, diphenylzinc, bis(pentafluorophenyl)zinc, 1 -propylzinc bromide, 2-propylzinc bromide, cyclobutylzinc bromide, cyclohexylzinc bromide, 4-cyanobutylzinc bromide, (1,3- dioxolan-2-ylmethyl)zinc bromide, phenethylzinc bromide, phenylzinc iodide, bis(pentafluorophenyl)zinc, benzylzinc bromide, methylzinc chloride, isobutylzinc bromide, 3-ethoxy-3-oxopropylzinc bromide, 1-adamantylzinc bromide, 4- methylbenzylzinc chloride, 2-(l,3-dioxolan-2-yl)]ethyl]zinc bromide, 2-thienylzinc bromide, 3, 5 -difluorobenzylzinc bromide, 4-methoxybenzylzinc chloride, 4- fluorobenzylzinc chloride, 2-adamantylzinc bromide, 3-butenylzinc bromide, 3-cyanopropylzinc bromide, a-methylbenzylzinc bromide, 6-ethoxy-6-oxohexylzinc bromide, 3-chlorobenzylzinc chloride, 2-fluorobenzylzinc chloride, 4- chlorobenzylzinc chloride, phenethylzinc bromide, 2,6-difluorophenylzinc bromide, 2-thiazolylzinc bromide, 2-ethylbutylzinc bromide, 6-methyl-2-pyridylzinc bromide, 5-ethoxy-5-oxopentylzinc bromide, 4-methyl-2-pyridylzinc bromide, (2-chloro-5- pyridyl)methylzinc chloride, 3-methoxybenzylzinc chloride, .sec-butylzinc bromide, 5-ethoxycarbonyl-2-fufurylzinc chloride, 2-cyanobenzylzinc bromide, 2- (ethoxycarbonyl)phenylzinc bromide, 4-bromo-2-fluorophenylzinc iodide, 4-[(4- morpholino)methyl]phenylzinc iodide, 2,5-difluoro-4-methoxyphenylzinc bromide, 4- cyanobenzylzinc bromide, 3 -methoxyphenylzinc iodide, 2, 3, 4,5,6- pentafluorobenzylzinc bromide, 5-bromo-2-methoxybenzylzinc chloride, 2- fluorophenylzinc iodide, 3-acetoxyphenylzinc iodide, 2,5-dichlorophenylzinc iodide, 4-acetoxyphenylzinc iodide, 2,6-difluorobenzylzinc bromide, 3-chloro-4- methylphenylzinc iodide, 4-ethoxybenzylzinc chloride, 2,6-dichlorobenzylzinc chloride, 2-pyridylzinc bromide, (2-naphthylmethyl)zinc bromide, and LiCl complexes and LiBr complexes thereof; that the first solvent is one or more selected from the list consisting of octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, and oligomeric poly(a-olefins) having from 2 to 6 repeating units, wherein said oligomeric poly(a-olefins) are optionally hydrogenated and selected from poly(l -decene), poly(l -undecene), poly(l -dodecene), poly(l-decene-co-l- octene), poly( 1 -decene-co- 1 -octene-co- 1 -dodecene), poly( 1 -dodecene-co- 1 -octene), poly(l-dodecene-co-l-decene), PAO283, PAO287, PAO432, and PAO687; that the second solvent is one or more selected from the list consisting of n-pcntanc, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, 2-methylpentane, 3- methylpentane, 2,2, -dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2- methylhexane, 3-methylhexane, 2,2, -dimethylpentane, 2,3-dimethylpentane, 2,4- dimethylpentane, 3,3-dimethylpetane, 3-ethylpentane, 2,2,3-trimethylbutane, cycloheptane, benzene, and toluene; and that the additive is selected from tertiary amine compounds having 3 to 15 carbon atoms, tertiary phosphine compounds having 3 to 15 carbon atoms, ether compoundshaving 4 to 10 carbon atoms, and sulfide compounds having 4 to 10 carbon atoms.

[0070] It is most preferred in the present invention that the organometallic compound is selected from the list consisting of methyllithium, ethyllithium, n- propyllithium, isopropyllithium, n-butyllithium, .sec-butyllithium, isobutyllithium, tert-butyllithium, n-hexyllithium, (trimethylsilyl)methyllithium, phenyllithium, trimethylaluminum, and diethylzinc; that the first solvent is one or more selected from the list consisting of decanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, and oligomeric poly(a-olefins) having from 2 to 6 repeating units, wherein said oligomeric poly(a- olefins) are optionally hydrogenated and selected from poly(l -decene), poly(l- decene- co - 1 -octene- co- 1 -dodecene) , and poly ( 1 -dodecene- co - 1 -decene) ; that the second solvent is one or more selected from the list consisting of / / -pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, / / -hexane, 2-methylpentane, 3- methylpentane, 2,2, -dimethylbutane, 2,3-dimethylbutane, cyclohexane, / / -heptane, 2- methylhexane, 3-methylhexane, 2,2, -dimethylpentane, 2,3-dimethylpentane, 2,4- dimethylpentane, 3,3-dimethylpetane, 3-ethylpentane, 2,2,3-trimethylbutane, cycloheptane, benzene, and toluene; and that the additive is selected from the list consisting of N,N,N’,N’ -tetramethylethylenediamine (TMEDA), N,N,N’,N”,N” -pentamethyldiethylenetriamine (PMDTA), tri- tert-butylphosphine, di- / e / 7-butyl ether, and di- / e / 7-butyl sulfide.Method for Preparation

[0071] In a second embodiment, the present invention provides a method for preparing a formulation according to the first embodiment, which method comprises mixing (a), (b), (c) and (d) in any order, wherein (a) is an organometallic compound;(b) is a first solvent, which is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 or more carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 or more carbon atoms or alkynes having 8 or more carbon atoms; (c) is a second solvent, which is one or more selected from aliphatic or aromatic hydrocarbons having 7 orless carbon atoms; and (d) is an additive selected from the list consisting of tertiary amines, tertiary phosphines, ethers and sulfides; characterized in that the additive is present in a stoichiometric or sub-stoichiometric amount with respect to the organometallic compound.

[0072] Preferred, more preferred, even more preferred, still even more preferred and most preferred organometallic compounds are the same as described above for the first embodiment of the present invention.

[0073] Preferred, more preferred, even more preferred, still even more preferred and most preferred first solvents are the same as described above for the first embodiment of the present invention.

[0074] Preferred, more preferred, even more preferred, still even more preferred and most preferred second solvents are the same as described above for the first embodiment of the present invention.

[0075] Preferred, more preferred, even more preferred, still even more preferred and most preferred additives are the same as described above for the first embodiment of the present invention.

[0076] It is to be understood that a skilled person can freely combine the above- mentioned preferred, more preferred, even more preferred, still even more preferred and / or most preferred embodiments relating to the first embodiment and to the second embodiment of the present invention.Use

[0077] In a third embodiment, the present invention relates to the use of a formulation according to the first embodiment as a reagent in chemical synthesis. It is preferred that the formulation is used as a reagent in an organic chemical synthesis, especially for the transfer of a metal or organic moiety to a substrate. Preferred organic chemical syntheses include reactions such as, for example, metal-halogen exchange reactions, deprotonation reactions of CH acidic compounds and / or NH containing compounds or nucleophilic addition reactions to carbonyl compounds or derivatives thereof, as base for traditional alkynylations or olefinations (Shapiroreactions, Julia olefinations, Peterson olefinations, or Wittig type reactions) or other class of C-H functionalization, as coupling partner for Murahashi type sp2-sp3coupling reactions.Effects and Benefits

[0078] In conclusion, the embodiments described herein overcome the disadvantages known from the prior art.

[0079] The formulations according to the first embodiment of the present invention are characterized by long-term stability, high reactivity, non-pyrophoricity, and low viscosity at room temperature. They are particularly suitable as reagents in synthesis having a good compatibility with liquid handlers and flow reactors, allowing an easy reaction work-up and product isolation, and offering an improved or at least similar reactivity compared to conventional organometallic reagents.

[0080] The formulations are non-pyrophoric and safer to handle. Generally, tertbutyllithium is considered as one of the most pyrophoric organolithium reagents under conventional conditions. The novel formulations of this is reagent is non- pyrophoric and can be easily handled even under open-air conditions. They also possess similar or improved reactivity for chemical transformations.

[0081] The formulations have a significantly reduced viscosity in comparison to non-formulated organolithium solutions known in the prior art. Notably, the reduction in viscosity renders the formulation compatible with automated liquid handling systems and flow reactors for the purposes of automation in chemical synthesis.

[0082] The formulations are characterized by an enhanced bench stability, wherein said formulations demonstrate superior resistance to molarity drops of the active organometallic species over time when compared to conventional organometallic solutions described in the prior art. Such improved bench stability offers excellent reliability when used in chemical synthesis and ensures consistently reproducible results.

[0083] The formulations are particularly suitable as reagents in synthesis having a good compatibility with liquid handlers and flow reactors, allowing an easy reactionwork-up and product isolation, and offering an improved or at least similar reactivity compared to conventional organometallic reagents.

[0084] The formulations facilitate chemical reactions with improved safety without sacrificing reactivity. Notably, the formulations enable chemical reactions under conditions that are proven to be safer than those required for conventional organometallic reagents, without sacrificing reactivity. When the formulations are used instead of the conventional reagents, the reaction results are often significantly improved, especially in selective nucleophilic addition reactions with multiple electrophilic centers and certain lithiation reactions.

[0085] The methods for preparing said formulations according to the second embodiment of the present invention allow a facile and scalable preparation of said multi-component formulations starting from commercially available, concentrated solutions of organometallic s without the necessity for solvent removal, which is a mandatory and arduous procedure in the methods described in the prior art.

[0086] The methods for preparing said formulations include a dilution step with further components, thereby simplifying the process for large-scale production and distinguishing the method from existing literature procedures in its efficiency and practicality in industrial applications.Definitions

[0087] As used herein, the term “about” or “approximately”, when used in connection with a measurable numerical variable, refers to the indicated value of the variable and to all values of the variable that are within the experimental error of the indicated value (e.g., within 95% confidence limit for the mean) or within ± 10%, preferably ± 5%, of the indicated value, whichever is greater.

[0088] As used herein, the term “polymer” or “polymeric” includes, but is not limited to, homopolymers, copolymers, for example, block, random, and alternating copolymers, terpolymers, quaterpolymers, etc., and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term shall include all possible configurational isomers of the molecule. These configurations include, but are not limited to isotactic, syndiotactic, and atactic symmetries. A polymer is a molecule ofhigh relative molecular mass, the structure of which essentially comprises the multiple repetition of units (i.e. repeating units) derived, actually or conceptually, from molecules of low relative mass (i.e. monomers).

[0089] As used herein, the term “oligomer” or “oligomeric” refers to a molecule that consists of a few repeating units which could be derived, actually or conceptually, from monomers. This is in contrast to a polymer, where the number of monomers is, in principle unlimited. Oligomers can be, for example, dimers, trimers, tetramers, pentamers, etc., which are composed of two, three, four, five, etc. monomers, respectively. However, it is to be understood that there is no sharp distinction between the concepts of oligomers and polymers. One proposed criterion is whether the molecule's properties vary significantly with the removal of one or a few of the repeating units.

[0090] As used herein, the term “monomer” refers to a molecule which can undergo polymerization thereby contributing constitutional units (repeating units) to the essential structure of a polymer or an oligomer.

[0091] As used herein, the term “copolymer” generally means any polymer derived from more than one species of monomer, wherein the polymer comprises more than one species of corresponding repeating unit. In one embodiment the copolymer is the reaction product of two or more species of monomer and thus comprises two or more species of corresponding repeating unit. It is preferred that the copolymer comprises two, three, four, five or six species of repeating unit. Copolymers that are obtained by copolymerization of three monomer species can also be referred to as terpolymers. Copolymers that are obtained by copolymerization of four monomer species can also be referred to as quaterpolymers. Copolymers may be present as block, random, and / or alternating copolymers.

[0092] As used herein, the term “block copolymer” refers to a copolymer, wherein adjacent blocks are constitutionally different, i.e. adjacent blocks comprise repeating units derived from different species of monomer or from the same species of monomer but with a different composition or sequence distribution of repeating units.

[0093] As used herein, the term “random copolymer” refers to a copolymer in which the probability of finding a given repeating unit at any given site in the chain isindependent of the nature of the adjacent repeating units. Usually, in a random copolymer, the sequence distribution of repeating units follows Bemoullian statistics.

[0094] As used herein, the term “alternating copolymer” refers to a copolymer consisting of macromolecules comprising two species of repeating units in alternating sequence.

[0095] “Poly(a-olefin)” or “PAO” is a collective term for synthetic hydrocarbon oils that are obtained from ethylene by means of polymerization. In this process, the ethylene is processes into a-olefins, of which, for example, the Cio and Cs / 12 parts are converted into a mixture of different oligomers on catalysts. Fractional distillation separates the crude oil into fractions with the required viscosities.

[0096] As used herein, the term “alkyl group” or “alkyl” refers to a saturated hydrocarbon moiety, such as, but not limited to, methyl, ethyl, propyl, and butyl. The alkyl group may be straight chain, branched chain or cyclic. For example, as used herein, propyl encompasses both / -propyl and isopropyl; butyl encompasses n-butyl, sec-butyl, isobutyl and tert-butyl, and so forth.

[0097] As used herein, the term “alkene” refers to an unsaturated hydrocarbon having at least one C=C double bond, such as, but not limited to, ethene, propene, butene, etc.. An alkene can be straight chain, branched chain or cyclic.

[0098] As used herein, the term “alkyne” refers to an unsaturated hydrocarbon having at least one C=C triple bond, such as, but not limited to, ethyne, propyne, butyne, etc.. An alkyne can be straight chain, branched chain or cyclic.

[0099] As used herein, the term “allyl” refers to a substituent with the structural formula R-CH2-CH=CH2, where R is any other group of atoms or H. It consists of a methylene bridge (-CH2-) attached to a vinyl group (-CH=CH2).

[0100] As used herein, the term “vinyl” refers to a substituent with the structural formula R-CH=CH2, where R is any other group of atoms or H.

[0101] The present invention is further illustrated by the examples following hereinafter which shall in no way be construed as limiting. A skilled person will acknowledge that various modifications, additions and alternations may be made tothe invention without departing from the spirit and scope of the invention as defined in the appended claims.ExamplesMaterials Used

[0102] PAO SpectraSyn™ 4 was obtained from Exxon Mobile. PAO SpectraSyn™ 4 is a mixture of (i) 1 -decene, homopolymer, hydrogenated; (ii) 1 -decene, polymer with 1 -octene and 1 -dodecene, hydrogenated; and (iii) 1 -dodecene, polymer with 1- decene, hydrogenated. All other components were obtained from Sigma- Aldrich.Viscosity Study

[0103] Viscosities of formulations of PAO SpectraSyn™ 4 and various amounts of hexanes (mixture of isomers, anhydrous, > 99%) (CAS: 107-83-5) at 20°C were measured and are shown in Table 1. The viscosities were measured with an Anton- Paar ViscoQC 300 viscometer equipped with a PTD 80 Peltier temperature control unit and a PT- 100 temperature probe using AP Connect software. The equipment was calibrated before measuring.

[0104] Table 1: Viscosities of formulations of PAO SpectraSyn™ 4 and hexanes at20°C.Preparation of Formulations

[0105] Example 1: Preparation of formulation with n-butyllithium (2.5 M)

[0106] Components used: organometallic compound: n-butyl lithium (n-BuLi); first solvent: PAO SpectraSyn™ 4 (80% v / v); second solvent: hexanes (mixture of isomers, anhydrous, > 99%) (20% v / v); additive: N,N,N’,N’ -tetramethylethylenediamine (TMEDA) (0.5 equiv.).

[0107] n-Butyllithium (2.5 M) (500 ml, 1.25 mol, 1.0 equiv.) was charged under inert conditions in a 1 L round-bottom flask equipped with a PTFE-coated stirring bar (note: suitable Schlenk techniques were applied for safer transfer). Then PAO SpectraSyn™ 4 (400 mL) was added, and the volatiles were removed under reduced pressure. After complete removal of the volatiles, the solution was further diluted with anhydrous hexanes (100 mL), and TMEDA (93.5 mL, 72.5 g, 0.62 mol, 0.5 equiv.) was added. The mixture was then stirred for 30 minutes. After obtaining a homogenous solution, the formulation was transferred to a 1 L sure-seal bottle underinert conditions (Formulation 1).

[0108] Pyrophoricity test

[0109] Formulation 1 (5 mL) was slowly dropped to a dry Kimwipe paper (or in water) in air. No vigorous reaction or smoking or fire was observed.

[0110] Example 2: Preparation of formulation with n-butyllithium (2.5 M)

[0111] Components used: organometallic compound: n-butyl lithium (n-BuLi); first solvent: PAO SpectraSyn™ 4 (80% v / v); second solvent: hexanes (mixture of isomers, anhydrous, > 99%) (20% v / v); additive: N,N,N’,N’ -tetramethylethylenediamine (TMEDA) (0.5 equiv.).

[0112] n-Butyllithium (2.5 M) (500 ml, 1.25 mol, 1.0 equiv.) was charged under inert conditions in a 1 L round-bottom flask equipped with a PTFE-coated stirring bar (note: suitable Schlenk techniques were applied for safer transfer). Then PAO SpectraSyn™ 4 (625 mL) was added, and the volatiles were removed under reduced pressure. After complete removal of the volatiles, the solution was further diluted with anhydrous hexanes (156 mL), and TMEDA (93.5 mL, 72.5 g, 0.62 mol, 0.5 equiv.) was added. The mixture was then stirred for 30 minutes. After obtaining a homogenous solution, the formulation was transferred to a 1 L sure-seal bottle under inert conditions (Formulation 2).

[0113] Pyrophoricity test

[0114] Formulation 2 (5 mL) was slowly dropped to a dry Kimwipe paper (or in water) in air. No vigorous reaction or smoking or fire was observed.

[0115] Example 3: Preparation of formulation with / e / 7-butyl lithium (1.7 M)

[0116] Components used: organometallic compound: / e / -butyl lithium (t-BuLi); first solvent: PAO SpectraSyn™ 4 (80% v / v); second solvent: hexanes (mixture of isomers, anhydrous, > 99%) (20% v / v); additive: N,N,N’,N’ -tetramethylethylenediamine (TMEDA) (0.5 equiv.).

[0117] tert-Butyllithium (1.7 M) (500 ml, 0.85 mol, 1.0 equiv.) was charged under inert conditions in a 1 L round-bottom flask equipped with a PTFE-coated stirring bar(note: suitable Schlenk techniques were applied for safer transfer). Then PAO SpectraSyn™ 4 (400 mL) was added, and the volatiles were removed under reduced pressure. After complete removal of the volatiles, the solution was further diluted with anhydrous hexanes (100 mL), and TMEDA (63.7 mL, 49.4 g, 0.425 mol, 0.5 equiv.) was added. The mixture was then stirred for 30 minutes. After obtaining a homogenous solution, the formulation was transferred to a 1 L sure-seal bottle under inert conditions (Formulation 3).

[0118] Pyrophoricity test

[0119] Formulation 3 (5 mL) was slowly dropped to a dry Kimwipe paper (or in water) in air. No vigorous reaction or smoking or fire was observed.

[0120] Example 4: Preparation of formulation with n-butyllithium (2.5 M)

[0121] Components used: organometallic compound: n-butyllithium (n-BuLi); first solvent: PAO SpectraSyn™ 4 (80% v / v); second solvent: hexanes (mixture of isomers, anhydrous, > 99%) (20% v / v); additive: tri- / e / 7-butylphosphinc ( / -BmP) (0.1 equiv.).

[0122] n-Butyllithium (2.5 M) (500 ml, 1.25 mol, 1.0 equiv.) was charged under inert conditions in a 1 L round-bottom flask equipped with a PTFE-coated stirring bar (note: suitable Schlenk techniques were applied for safer transfer). Then PAO SpectraSyn™ 4 (400 mL) was added, and the volatiles were removed under reduced pressure. After complete removal of the volatiles, the solution was further diluted with anhydrous hexanes (100 mL), and t-BuaP (25.2 g, 0.125 mol, 0.1 equiv.) was added. The mixture was then stirred for 30 minutes. After obtaining a homogenous solution, the formulation was transferred to a 1 L sure-seal bottle under inert conditions (Formulation 4).

[0123] Pyrophoricity test

[0124] Formulation 4 (5 mL) was slowly dropped to a dry Kimwipe paper (or inwater) in air. No vigorous reaction or smoking or fire was observed.

[0125] Example 5: Preparation of formulation with n-butyllithium (2.5 M)

[0126] Components used: organometallic compound: n-butyl lithium (n-BuLi); first solvent: PAO SpectraSyn™ 4 (80% v / v); second solvent: hexanes (mixture of isomers, anhydrous, > 99%) (20% v / v); additive: N,N,N’,N’ -tetramethylethylenediamine (TMEDA) (0.1 equiv.).

[0127] n-Butyllithium (2.5 M) (500 ml, 1.25 mol, 1.0 equiv.) was charged under inert conditions in a 1 L round-bottom flask equipped with a PTFE-coated stirring bar (note: suitable Schlenk techniques were applied for safer transfer). Then PAO SpectraSyn™ 4 (400 mL) was added, and the volatiles were removed under reduced pressure. After complete removal of the volatiles, the solution was further diluted with anhydrous hexanes (100 mL), and TMEDA (14.5 g, 0.125 mol, 0.1 equiv.) was added. The mixture was then stirred for 30 minutes. After obtaining a homogenous solution, the formulation was transferred to a 1 L sure-seal bottle under inert conditions (Formulation 5).

[0128] Pyrophoricity test

[0129] Formulation 5 (5 mL) was slowly dropped to a dry Kimwipe paper (or in water) in air. No vigorous reaction or smoking or fire was observed.

[0130] Example 6: Preparation of formulation with n-butyllithium (2.5 M)

[0131] Components used: organometallic compound: n-butyl lithium (n-BuLi); first solvent: hexadecane (80% v / v); second solvent: hexanes (mixture of isomers, anhydrous, > 99%) (20% v / v); additive: tri-tert-butylphosphine ( / -BmP) (0.1 equiv.).

[0132] n-Butyllithium (2.5 M) (500 ml, 1.25 mol, 1.0 equiv.) was charged under inert conditions in a 1 L round-bottom flask equipped with a PTFE-coated stirring bar (note: suitable Schlenk techniques were applied for safer transfer). Then hexadecane (400 mL) was added, and the volatiles were removed under reduced pressure. After complete removal of the volatiles, the solution was further diluted with anhydrous hexanes (100 mL), and t-BuaP (25.2 g, 0.125 mol, 0.1 equiv.) was added. The mixture was then stirred for 30 minutes. After obtaining a homogenous solution, theformulation was transferred to a 1 L sure- seal bottle under inert conditions (Formulation 6).

[0133] Pyrophoricity test

[0134] Formulation 6 (5 mL) was slowly dropped to a dry Kimwipe paper (or in water) in air. No vigorous reaction or smoking or fire was observed.Application of Formulations in Organic Syntheses

[0135] Example 7: Nucleophilic addition of n-butyl lithium to aldehydeFormulation 1 or Formulation 2

[0136] A 20 mL vial was charged with aldehyde 1 (136 mg, 1.0 mmol), and a stirring bar. The container was evacuated and filled with nitrogen; this cycle was repeated three additional times. Later, the aldehyde was dissolved in THE (5 mL) and cooled to -10°C. Live minutes later, Formulation 1 (0.4 mL, 1.0 mmol) or Formulation 2 (0.6 mL, 1.0 mmol) was added over 5 minutes. The mixture was stirred for 1 h, while the temperature was allowed to rise to room temperature. The conversion was monitored after quenching the reaction with water. The reactionconversions for product 2 were determined by GC (see Table 2).

[0137] Table 2: Reaction conversions determined by GC for Example 7.

[0138] Example 8: Lithium-halogen exchangeFormulation 1, Formulation 2

[0139] A 20 mL vial was charged with aryl halide 3 (231 mg, 1.0 mmol), and a stirring bar. The container was evacuated and filled with nitrogen; this cycle was repeated three additional times. Later, the aryl halide was dissolved in THF (5 mL) and cooled to -78°C. Five minutes later, Formulation 1 (0.4 mL, 1.0 mmol) or Formulation 2 (0.6 mL, 1.0 mmol) or Formulation 3 (0.6 mL, 1.0 mmol) was added over 5 minutes. The mixture was stirred for 2 h, while the temperature was allowed to rise to room temperature. The conversion was monitored after quenching the reaction with water. The reaction conversions for product 4 were determined by GC (see Table

[0140] Table 3: Reaction conversions determined by GC for Example 8.

[0141] Example 9: Lithium-halogen exchangeFormulation 3 (1.1 equiv.)PAd25 6

[0142] A 50 mL Schlenk-flask was charged with aryl halide 5 (1000 mg, 5.0 mmol), and a stirring bar. The container was evacuated and filled with nitrogen; this cycle was repeated three additional times. Later, the aryl halide was dissolved in THF (25 mL) and cooled to -78°C. Ten minutes later, Formulation 3 (3.1 mL, 5.5 mmol) was added over 10 minutes. The mixture was stirred for 2 h at -78°C. Later, a 1.0 M THF solution of AdiPCI (6.0 mL) was added over 15 minutes. The mixture was stirred overnight. After 16 h the reaction was quenched by the addition of anhydrous MeOH. Product 6 was crashed from the reaction mixture. The product was collected by simple vacuum filtration (1.6 g, 77%).

[0143] Example 10: Selective nucleophilic addition reaction

[0144] A 20 mL vial was charged with aldehyde 7 (185 mg, 1.0 mmol), and astirring bar. The container was evacuated and filled with nitrogen; this cycle was repeated three additional times. Later, the aldehyde was dissolved in THF (5 mL) and cooled to 0°C. Five minutes later, Formulation 1 (1.0 mmol) or commercially available 2.5 M n-BuLi solution in hexanes (1.0 mmol) was added over 5 minutes. The mixture was stirred for 2 h, while the temperature was allowed to rise to room temperature. The conversion was monitored after quenching the reaction with MeOH. The reaction conversions were determined by GCMS (see Table 4).

[0145] Table 4: Reaction conversions determined by GCMS for Example 10.

[0146] The examples mentioned above demonstrate the superior safety, reactivity and selectivity of the formulations according to the invention compared to standard organometallic reagents.

[0147] Example 11: Kinetic study of lithium-halogen exchangeH

[0148] Twenty-four 7 mL vials were charged with aryl halide 11 (93.5 mg, 0.5 mmol), and a stirring bar. The container was evacuated and filled with nitrogen; this cycle was repeated three additional times. Later, the aryl halide was dissolved in THF (2 mL) and cooled to -78°C. Five minutes later, Formulation 4 or 5 or n-BuLi in PAG SpectraSyn™ 4 (2.5 M) or commercially available 2.5 M n-BuLi solution in hexanes (0.5 mmol) was added over 5 minutes (6 reactions vials for each n-BuLi variations). All the reaction mixture were stirred after addition at -78°C. Each vial from individual sets (1 out of every 6 vials for each formulations) were quenched withanhydrous MeOH (1.0 mL) at the respective time intervals (5, 10, 15, 20, 25, and 30 mins.). Aliquots from the quenched reactions were analyzed using GC.

[0149] Table 5: Kinetic study with different formulations and comparison with commercially available 2.5 M n-BuLi in hexanes (GC conversions are summarized in the table).

[0150] The results in Table 5 above indicate that Formulations 4 and 5 exhibit enhanced reactivity in lithium-halogen exchange compared to conventional lithiation formulations.References

[0151] [1] P. Powell, Principles of Organometallic Chemistry, Springer Link, 1988.

[0152] [2] T. Klatt, J.T. Markiewicz, C. Samann, P. Knochel, J. Org. Chem. 2014,79, 4253-4269.

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[0155] [5] S. Saito, Aluminum in Organic Synthesis, Main Group Metals inOrganic Synthesis, 2004, 189-306.

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Claims

We claim:

1. Formulation comprising:(a) an organometallic compound;(b) a first solvent, which is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 or more carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 or more carbon atoms or alkynes having 8 or more carbon atoms;(c) a second solvent, which is one or more selected from aliphatic or aromatic hydrocarbons having 7 or less carbon atoms; and(d) an additive selected from the list consisting of tertiary amines, tertiary phosphines, ethers and sulfides; characterized in that the additive is present in a stoichiometric or sub-stoichiometric amount with respect to the organometallic compound.

2. Formulation according to claim 1, wherein the organometallic compound is selected from the list consisting of organolithium compounds, organomagnesium compounds, organoaluminum compounds, and organozinc compounds.

3. Formulation according to claim 1 or 2, wherein the organometallic compound comprises one or more saturated or unsaturated aliphatic moieties, saturated or unsaturated alicyclic moieties, aromatic moieties, heteroaromatic moieties or combinations thereof, which optionally comprise independently from each other one or more substituents selected from the list consisting of -F, -Cl, -Br, -CN, -CF3, -CeFs, -OCH3, -OCF3, -OC6H5, -OCH2C6H5, -N(CH3)2, -N[Si(CH3)3]2, -Si(CH3)3, -Si(CF3)3, 1,3-dioxolan, and 1,3-dioxan, wherein the heteroaromatic moieties comprise independently from each other one or more heteroatoms selected from N, O, and S, preferably S.

4. Formulation according to any one of claims 1 to 3, wherein the organometallic compound is optionally present as an alkali metal halide salt complex, preferably as an alkali metal fluoride salt complex, alkali metal chloride salt complex, alkali metal bromide salt complex, or alkali metal iodide salt complex, more preferably as an alkali metal chloride salt complex or alkali metal bromide salt complex.

5. Formulation according to any one of claims 1 to 4, wherein the organometallic compound is selected from the list consisting of(1) methyllithium, ethyllithium, n -propyllithium, isopropyllithium, n -butyllithium, sec-butyllithium, isobutyllithium, tert-butyllithium, n -hexyllithium, (trimethylsilyl)methyllithium, and phenyllithium;(2) methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium chloride, n-propylmagnesium bromide, isopropylmagnesium chloride, isopropylmagnesium bromide, cyclopropylmagnesium chloride, cyclopropylmagnesium bromide, n-butylmagncsium chloride, n-butylmagncsium bromide, sec-butylmagnesium chloride, .sec-butylmagncsium bromide, isobutylmagnesium chloride, isobutylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, n-pcntylmagncsium chloride, n- pentylmagnesium bromide, 1,1 -dimethylpropylmagnesium chloride, cyclopentylmagnesium chloride, cyclopentylmagnesium bromide, 2,2- dimethylpropylmagnesium chloride, 2,2-dimethylpropylmagnesium bromide, hexylmagnesium chloride, hexylmagnesium bromide, cyclohexylmagnesium chloride, cyclohexylmagnesium bromide, heptylmagnesium chloride, heptylmagnesium bromide, octylmagnesium chloride, octylmagnesium bromide, (2- ethylhexyl)magnesium chloride, (2-ethylhexyl)magnesium bromide, nonylmagnesium chloride, nonylmagnesium bromide, decylmagnesium chloride, decylmagnesium bromide, 3,7-dimethyloctylmagnesium chloride, 3,7-dimethyloctylmagnesium bromide, dodecylmagnesium chloride, dodecylmagnesium bromide, tetradecylmagnesium chloride, tetradecylmagnesium bromide, pentadecylmagnesium chloride, pentadecylmagnesium bromide, octadecylmagnesium chloride, octadecylmagnesium bromide, (cyclohexylmethyl)magnesium chloride, (cyclohexylmethyl)magnesium bromide, phenethylmagnesium chloride,phenethylmagnesium bromide, (trimethylsilyl)methylmagnesium chloride, (trimethylsilyl)methylmagnesium bromide, 2-methyl-2-phenylpropylmagnesium chloride, 2-methyl-2-phenylpropylmagnesium bromide, benzylmagnesium chloride, benzylmagnesium bromide, 3-methylbenzylmagnesium chloride, 3- methylbenzylmagnesium bromide, 4-methylbenzylmagnesium chloride, 4- methylbenzylmagnesium bromide, 2-methoxybenzylmagnesium chloride, 2- methoxybenzylmagnesium bromide, 3-methoxybenzylmagnesium chloride, 3- methoxybenzylmagnesium bromide, 4-methoxybenzylmagnesium chloride, 4- methoxybenzylmagnesium bromide, 4-fluorobenzylmagnesium chloride, 4- fluorobenzylmagnesium bromide, 2-bromobenzylmagnesium chloride, 2- bromobenzylmagnesium bromide, 3-bromobenzylmagnesium chloride, 3- bromobenzylmagnesium bromide, (l,3-dioxolan-2-ylmethyl)magnesium bromide, (l,3-dioxan-2-ylethyl)magnesium bromide, vinylmagnesium chloride, vinylmagnesium bromide, ethynylmagnesium chloride, ethynylmagnesium bromide, allylmagnesium chloride, allylmagnesium bromide, 2-methylallylmagnesium chloride, 2-methylallylmagnesium bromide, isopropenylmagnesium chloride, isopropenylmagnesium bromide, 1-propynylmagnesium chloride, 1- propynylmagnesium bromide, 1 -methyl- 1 -propenylmagnesium chloride, 1 -methyl- 1- propenylmagnesium bromide, l-methyl-2-propenylmagnesium chloride, l-methyl-2- propenylmagnesium bromide, 2-methyl-l -propenylmagnesium chloride, 2-methyl-l- propenylmagnesium bromide, 3-butenylmangnesium chloride, 3-butenylmangnesium bromide, 4-pentenylmagnesium chloride, 4-pentenylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, pentafluorophenylmagnesium bromide, -tolylmagncsium chloride, -tolylmagncsium bromide, o-tolylmagnesium chloride, o-tolylmagnesium bromide, 2,3- dimethylphenylmagnesium bromide, 2,5-dimethylphenylmagnesium bromide, 2,6- dimethylphenylmagnesium bromide (= 2-mesitylmagnesium bromide), 3,5- dimethylphenylmagnesium bromide, 3,5-bis(trifluoromethyl)phenylmagnesium bromide, 4-isopropylphenylmagnesium bromide, 2,4,6-triisopropylphenylmagnesium bromide, 4-tert-butylphenylmagnesium bromide, 2-methoxyphenylmagnesium bromide, 3-methoxyphenylmagnesium bromide, 4-methoxyphenylmagnesium bromide, 4-(trifluoromethoxy)phenylmagnesium bromide, 4-methoxy-2- methylphenylmagnesium bromide, 2,4-dimethoxyphenylmagnesium bromide, 3,4- dimethoxyphenylmagnesium bromide, 3,5-dimethoxyphenylmagnesium chloride, 3,5-dimethoxyphenylmagnesium bromide, 3,4,5-trimethoxyphenylmagnesium bromide, 4-phenoxyphenylmagnesium bromide, 3-fluorophenylmagnesium bromide, 4- fluorophenylmagnesium bromide, 4-fluoro-2-methylphenylmagnesium bromide, 3,4- difluorophenylmagnesium bromide, 3,5-difluorophenylmagnesium bromide, 3- chlorophenylmagnesium bromide, 4-chlorophenylmagnesium bromide, 3,4- dichlorophenylmagnesium bromide, 3,5-dichlorophenylmagnesium bromide, 3- chloro-4-fluorophenylmagnesium bromide, 4-chloro-3-fluorophenylmagnesium bromide, 2-benzyloxyphenylmagnesium bromide, 4-benzyloxyphenylmagnesium bromide, (4- / V-di methyl) aniline magnesium bromide, 3- [bis(trimethylsilyl)amino)phenylmagnesium chloride, 3- [bis(trimethylsilyl)amino)phenylmagnesium bromide, 4- [bis(trimethylsilyl)amino]phenylmagnesium chloride, 4- [bis(trimethylsilyl)amino]phenylmagnesium bromide, 1 -naphthylmagnesium bromide, 2-naphthylmagnesium bromide, 2-biphenylmagnesium bromide, 4- biphenylmagnesium bromide, 9-phenanthrylmagnesium bromide, 3-methyl-2- thienylmagnesium bromide, 2-thienylmagnesium bromide, 3 -thienylmagnesium iodide, di-n-butylmagnesium, divinylmagnesium, diphenylmagnesium, and LiCl complexes and LiBr complexes thereof;(3) trimethylaluminum, triisobutylaluminum, methylaluminoxane, triethylaluminum, bis(trimethylaluminum)- 1 ,4-diazabicyclo[2.2.2]octane adduct, diethylaluminum chloride, ethylaluminum dichloride, trioctylaluminum, diethylaluminum chloride, diethylaluminum cyanide, triphenylaluminum, diethylaluminum ethoxide, diisobutylaluminum chloride, lithium diisobutyl-tert-butoxyaluminum hydride, diisobutyl aluminum hydride, and LiCl complexes and LiBr complexes thereof; and(4) dimethylzinc, diethylzinc, diisopropyl zinc, diphenylzinc, bis(pentafluorophenyl)zinc, 1 -propylzinc bromide, 2-propylzinc bromide, cyclobutylzinc bromide, cyclohexylzinc bromide, 4-cyanobutylzinc bromide, (1,3- dioxolan-2-ylmethyl)zinc bromide, phenethylzinc bromide, phenylzinc iodide, bis(pentafluorophenyl)zinc, benzylzinc bromide, methylzinc chloride, isobutylzinc bromide, 3-ethoxy-3-oxopropylzinc bromide, 1-adamantylzinc bromide, 4- methylbenzylzinc chloride, 2-(l,3-dioxolan-2-yl)]ethyl]zinc bromide, 2-thienylzinc bromide, 3, 5 -difluorobenzylzinc bromide, 4-methoxybenzylzinc chloride, 4-fluorobenzylzinc chloride, 2-adamantylzinc bromide, 3-butenylzinc bromide, 3- cyanopropylzinc bromide, a-methylbenzylzinc bromide, 6-ethoxy-6-oxohexylzinc bromide, 3-chlorobenzylzinc chloride, 2-fluorobenzylzinc chloride, 4- chlorobenzylzinc chloride, phenethylzinc bromide, 2,6-difluorophenylzinc bromide, 2-thiazolylzinc bromide, 2-ethylbutylzinc bromide, 6-methyl-2-pyridylzinc bromide, 5-ethoxy-5-oxopentylzinc bromide, 4-methyl-2-pyridylzinc bromide, (2-chloro-5- pyridyl)methylzinc chloride, 3-methoxybenzylzinc chloride, .sec-butylzinc bromide, 5-ethoxycarbonyl-2-fufurylzinc chloride, 2-cyanobenzylzinc bromide, 2- (ethoxycarbonyl)phenylzinc bromide, 4-bromo-2-fluorophenylzinc iodide, 4-[(4- morpholino)methyl]phenylzinc iodide, 2,5-difluoro-4-methoxyphenylzinc bromide, 4- cyanobenzylzinc bromide, 3 -methoxyphenylzinc iodide, 2, 3, 4,5,6- pentafluorobenzylzinc bromide, 5-bromo-2-methoxybenzylzinc chloride, 2- fluorophenylzinc iodide, 3-acetoxyphenylzinc iodide, 2,5-dichlorophenylzinc iodide, 4-acetoxyphenylzinc iodide, 2,6-difluorobenzylzinc bromide, 3-chloro-4- methylphenylzinc iodide, 4-ethoxybenzylzinc chloride, 2,6-dichlorobenzylzinc chloride, 2-pyridylzinc bromide, (2-naphthylmethyl)zinc bromide, and LiCl complexes and LiBr complexes thereof.

6. Formulation according to any one of claims 1 to 5, wherein the organometallic compound is selected from the list consisting of methyllithium, ethyllithium, n- propyllithium, isopropyllithium, n -butyllithium, .sec-butyllithium, isobutyllithium, tert-butyllithium, n -hexyllithium, (trimethylsilyl)methyllithium, phenyllithium, trimethylaluminum, and diethylzinc.

7. Formulation according to any one of claims 1 to 6, wherein the first solvent is selected from one or more of monomeric linear chain, branched chain or cyclic hydrocarbons having 8 to 20 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 to 20 carbon atoms or alkynes having 8 to 20 carbon atoms.

8. Formulation according to any one of claims 1 to 6, wherein the first solvent is selected from one or more of monomeric linear chain, branched chain or cyclic hydrocarbons having 8 to 16 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 20 repeating units, which in each occurrence are independently from eachother derived from alkenes having 8 to 16 carbon atoms or alkynes having 8 to 16 carbon atoms.

9. Formulation according to any one of claims 1 to 6, wherein the first solvent is selected from one or more of monomeric linear chain, branched chain or cyclic hydrocarbons having 9 to 12 carbon atoms; and / or oligomeric hydrocarbons having from 2 to 10 repeating units, which in each occurrence are independently from each other derived from alkenes having 9 to 12 carbon atoms or alkynes having 9 to 12 carbon atoms.

10. Formulation according to any one of claims 1 to 6, wherein the first solvent is one or more selected from the list consisting of octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, and oligomeric poly(a-olefins) having from 2 to 6 repeating units, which in each occurrence are independently from each other derived from alkenes having 9 to 12 carbon atoms or alkynes having 9 to 12 carbon atoms.

11. Formulation according to any one of claims 1 to 6, wherein the first solvent is one or more selected from the list consisting of octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, and oligomeric poly(a-olefins) having from 2 to 6 repeating units, wherein said oligomeric poly(a- olefins) are optionally hydrogenated and selected from poly(l -decene), poly(l- undecene), poly(l -dodecene), poly(l-decene-co-l-octene), poly(l-decene-co-l- octene-co- 1 -dodecene), poly( 1 -dodecene-co- 1 -octene), poly( 1 -dodecene-co- 1 - decene), PAO283, PAO287, PAO432, and PAO687.

12. Formulation according to any one of claims 1 to 11, wherein the second solvent is one or more selected from aliphatic linear chain, branched chain or cyclic hydrocarbons having 5 to 7 carbon atoms or aromatic hydrocarbons having 6 or 7 carbon atoms.

13. Formulation according to any one of claims 1 to 12, wherein the second solvent is one or more selected from the list consisting of n-pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane,2, 2, -dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-heptane, 2-methylhexane, 3- methylhexane, 2,2, -dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpetane, 3-ethylpentane, 2,2,3-trimethylbutane, cycloheptane, benzene and toluene.

14. Formulation according to any one of claims 1 to 13, wherein the additive is selected from tertiary amine compounds having 3 to 30 carbon atoms, tertiary phosphine compounds having 3 to 30 carbon atoms, ether compounds having 4 to 30 carbon atoms, and sulfide compounds having 2 to 30 carbon atoms.

15. Formulation according to any one of claims 1 to 13, wherein the additive is selected from tertiary amine compounds having 3 to 24 carbon atoms, tertiary phosphine compounds having 3 to 24 carbon atoms, ether compounds having 2 to 20 carbon atoms, and sulfide compounds having 2 to 20 carbon atoms.

16. Formulation according to any one of claims 1 to 13, wherein the additive is selected from tertiary amine compounds having 3 to 15 carbon atoms, tertiary phosphine compounds having 3 to 15 carbon atoms, ether compounds having 4 to 10 carbon atoms, and sulfide compounds having 4 to 10 carbon atoms.

17. Formulation according to any one of claims 1 to 16, wherein the additive is selected from the list consisting of N,N,N’,N’ -tetramethylethylenediamine (TMEDA),N,N,N’,N”,N” -pentamethyldiethylenetriamine (PMDTA), tri- tert-butyl phosph ine, di- tert-butyl ether, and di- tert-butyl sulfide.

18. Formulation according to any one of claims 1 to 17, wherein the molar ratio of the additive to the organometallic compound in the formulation is in the range fromO.0000001:1 (100 ppb) to 1:1, preferably from 0.01: 1 to 1:1, even preferably from 0.1:1 to 0.9:1, more preferably from to 0.3:1 to 0.7:1, even more preferably from 0.4:1 to 0.6: 1 , and most preferably about 0.1:1 or about 0.5:1.

19. Formulation according to any one of claims 1 to 18, wherein the volume ratio of the first solvent to the second solvent in the formulation is in the range from 50:50 to 99:1, preferably from 50:50 to 95:5, more preferably from 65:35 to 90:10, even more preferably from 75:25 to 85:15, and most preferably about 80:20.

20. Formulation according to any one of claims 1 to 19, wherein the concentration of the organometallic compound in the formulation is in the range from 0.01 mol / L to12 mol / L, preferably from 0.1 mol / L to 6.0 mol / L, more preferably from 0.2 mol / L to 5.0 mol / L, even more preferably from 0.5 to 4.0 mol / L, and most preferably from 0.5 mol / L to 3.0 mol / L.

21. Method for preparing a formulation according to any one of claims 1 to 20, which method comprises mixing (a), (b), (c) and (d) in any order, wherein (a) is an organometallic compound; (b) is a first solvent, which is one or more selected from monomeric linear chain, branched chain or cyclic hydrocarbons having 8 or more carbon atoms; and / or oligomeric hydrocarbons having from 2 to 30 repeating units, which in each occurrence are independently from each other derived from alkenes having 8 or more carbon atoms or alkynes having 8 or more carbon atoms; (c) is a second solvent, which is one or more selected from aliphatic or aromatic hydrocarbons having 7 or less carbon atoms; and (d) is an additive selected from the list consisting of tertiary amines, tertiary phosphines, ethers and sulfides; characterized in that the additive is present in a stoichiometric or sub-stoichiometric amount with respect to the organometallic compound.

22. Use of a formulation according to any one of claims 1 to 20 as a reagent in chemical synthesis.

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