Chiral sulfoxide alkene ligand, preparation method and application thereof

A sulfoxide and ligand technology, which is applied to chiral sulfoxide ligands and the fields of preparation and application thereof, can solve problems such as no literature reports, and achieve the effects of easy storage, mild synthesis conditions and short synthesis routes.

Inactive Publication Date: 2012-11-21
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
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Problems solved by technology

[0008] At present, the application of chiral diene, phosphine, and nitrene ligands is mainly concentrated on Rh(I)-catalyzed 1,4-conjugate addition and Ir(I)-catalyzed hydrogenation reaction, and the expansion and reaction of substrates The extension of the type needs to be further studied (for example, the substrates are mostly limited to the conjugate addition of p-cyclic enone and

Method used

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  • Chiral sulfoxide alkene ligand, preparation method and application thereof
  • Chiral sulfoxide alkene ligand, preparation method and application thereof
  • Chiral sulfoxide alkene ligand, preparation method and application thereof

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Embodiment Construction

[0024] Taking ligand 1c in Formula 1 as an example, the synthetic route is as in Formula 7:

[0025]

[0026] The synthetic route of formula 7 chiral sulfoxide ene ligand 1c

[0027] Scheme 1.Synthesis of olefin-sulfoxide ligand 1c.Reagents and conditions: a) P(OEt)3, 160℃, 5h; b) NaH, THF, 0℃to room temperature, 1h; then4-fluorobenzaldehyde, THF, 0℃ to room temperature, overnight, 89%; c) n-BuLi, THF, -78°C; then(R)-thiosulfinate, THF, -78°C to room temperature, overnight, 52.3%.

[0028] The specific operation steps are as follows:

[0029] a): With reference to the literature [Blake, Alexander J.; Harding, Mervyn; Sharp, John T.;. ) into 0.14 mol of triethyl phosphite, slowly heated to 160°C, heated for 5 hours, cooled to room temperature, and slowly distilled under reduced pressure to obtain 33.6g of colorless oily liquid (130-132°C, 1mmHg). Yield 92%.

[0030] b): Under argon atmosphere, put 1mmol o-bromobenzyl phosphite diethyl (B) into 2ml of THF, slowly add 1.2m...

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Abstract

The invention relates to a chiral sulfoxide alkene ligand, a preparation method and an application thereof. According to the present invention, cheap and available 2-bromobenzyl bromide is adopted as a start material to obtain 2-bromobenzyl diethyl phosphate; then a Horner-Emmons reaction is adopted to introduce an alkene group; and finally lithiation modification is performed on bromine, and a corresponding chiral sulfoxide group is introduced. With the present invention, the target product is conveniently and rapidly synthesized through three steps; coordinate of the novel chiral sulfoxide alkene ligand and rhodium can be well used for catalysis of conjugate addition reactions on cyclic ketene, nitroalkene, and cyano alkene by aryl boronic acid, especially for an addition reaction on cyclic ketene by aryl boronic acid, wherein a good catalysis effect of the addition reaction on the cyclic ketene by the aryl boronic acid is provided.

Description

technical field [0001] The invention relates to the design of a novel chiral sulfoxidene ligand and the preparation method of the ligand. It also relates to the application of the above-mentioned ligands in catalyzing the conjugate addition reaction of aryl boronic acid to cyclic enones, nitroalkenes and cyanoalkenes. Background technique [0002] In chiral metal catalysis, one of the core issues is the ingenious design and synthesis of excellent chiral ligands. Over the years, people have achieved great success in the synthesis of various chiral ligands and have been widely used in asymmetric catalytic reactions. For example, the well-known sulfur ligands play an important role in asymmetric catalytic reactions [Document 1. (a) Masdeu-Bultü, A.M; Déguez, M; Maryin, E.; Gümez, M.Coord.Chem.Rev .2003, 242, 159. (b) Fernández, I. Khiar, N. Chem. Rev. 2003, 103, 3651. (c) Mellah, M.; Voituriez, A.; Schulz, E. Chem. Rev. 2007 , 107, 5133. Literature 2. (a) Wang, C.; Wu, X.; Z...

Claims

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Application Information

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IPC IPC(8): C07C317/14C07C317/22C07C317/24C07C315/00B01J31/22C07C49/657C07C45/68C07C205/32C07C201/12C07C255/37C07C253/30
Inventor 万伯顺薛峰吴凡
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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