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Metallocene-based chiral phosphine or arsine ligands

A ligand, metallocene technology, applied in the field of metal ligand complexes, to achieve the effect of a large selection range

Inactive Publication Date: 2007-02-14
SOLVIAS AG
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0018] Another class of known diphosphine ligands shows chirality only at the phosphorus atom:

Method used

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  • Metallocene-based chiral phosphine or arsine ligands
  • Metallocene-based chiral phosphine or arsine ligands
  • Metallocene-based chiral phosphine or arsine ligands

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0149] (R c , S Fe , S P )-2-[(1-N, N-dimethylamino)ethyl]-1-[(2-methoxyphenyl)phenylphosphino]ferrocene[(R c , S Fe , S p )-2]:

[0150]

[0151]Et 2 To a solution of O (50 mL) was added 1.7M t-BuLi in pentane (9.7 mL, 16.5 mmol) over 10 minutes. After complete addition, the mixture was warmed to room temperature and stirred at room temperature for 1.5 hours. The resulting red solution was recooled to -78°C, followed by the addition of dichlorophenylphosphine (2.24 mL, 16.5 mmol) in one portion. After stirring at -78°C for 10 minutes, the mixture was slowly warmed to room temperature and stirred at room temperature for 1.5 hours. The mixture was recooled to -78°C, followed by the slow addition of (2-methoxy)phenyllithium solution [from 2-bromomethoxybenzene (3.32 g, 17.7 mmol) and 1.7 M t-BuLi in pentane Solution (20.8mL, 35.4mmol) in Et 2 O (90mL), prepared by reaction at -78°C]. The mixture was warmed to room temperature overnight, then filtered through a pad ...

Embodiment 2

[0153] (R c , S Fe , S P )-2-[(1-N, N-dimethylamino)ethyl]-1-[(1-naphthyl)phenylphosphino]ferrocene[(R c , S Fe , S p )-3]:

[0154]

[0155] Et 2 To a solution of O (60 mL) was added 1.7M t-BuLi in pentane (12.94 mL, 22 mmol) over 10 minutes. After complete addition, the mixture was warmed to room temperature and stirred at room temperature for 1.5 hours. The resulting red solution was recooled to -78°C, then dichlorophenylphosphine (2.99 mL, 22 mmol) was added in one portion. After stirring at -78°C for 10 minutes, the mixture was slowly warmed to room temperature and stirred at room temperature for 1.5 hours. The mixture was recooled to -78 °C, followed by the slow addition of 1-naphthalenelithium solution [from 1-bromonaphthalene (5.38 g, 26 mmol) and 1.7M t-BuLi in pentane (30.6 mL, 52 mmol) in Et 2 O (120mL), prepared by reaction at -78°C]. The mixture was warmed to room temperature overnight, then filtered through a pad of Celite. The filtrate was concentr...

Embodiment 3

[0157] (R c , S Fe , S P )-2-[(1-N, N-dimethylamino)ethyl]-1-[(1-naphthyl)phenylphosphino]ferrocene[(R c , S Fe , S p )-3] and (R c , S Fe , R P )-2-[(1-N, N-dimethylamino)ethyl]-1-[(1-naphthyl)phenylphosphino]ferrocene[(R c , S Fe , R p )-4]:

[0158]

[0159] Et 2 To a solution of O (15 mL) was added 1.7M t-BuLi in pentane (3.2 mL, 5.5 mmol) over 10 minutes. After complete addition, the mixture was warmed to room temperature and stirred at room temperature for 1.5 hours. The resulting red solution was recooled to -78°C, then dichlorophenylphosphine (0.75 mL, 5.5 mmol) was added in one portion. After stirring at -78°C for 10 minutes, the mixture was slowly warmed to room temperature and stirred at room temperature for 1.5 hours. 1-Naphthyllithium solution [from 1-bromonaphthalene (1.35 g, 6.5 mmol) and 1.7M t-BuLi in pentane (7.6 mL, 13 mmol) in Et 2 O (30mL), prepared by reaction at -78°C]. The mixture was stirred overnight at room temperature, then filter...

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Abstract

The present invention relates to metallocene-based phosphine ligands having chirality at phosphorus and at least one other element of chirality (planar chirality and / or chirality at carbon); and to the use of such ligands in asymmetric transformation reactions to generate high enantiomeric excesses of formed compounds. A method for the preparation of ligands according to the invention involving the conversion of the ortho-lithiated substituted metallocene to a phosphine chiral at phosphorus is also disclosed.

Description

technical field [0001] The present invention relates to novel metallocene-based phosphine ligands and methods for their preparation which incorporate up to four chiral elements, namely planar, phosphorous, and optionally carbochiral and axial Chirality. The present invention also relates to metal ligand complexes which can be used as catalysts or catalyst precursors in asymmetric transformation reactions to give products in high enantiomeric excess. Arsines of similar structure are also within the scope of the present invention. Background technique [0002] Ferrocenes as a framework for diphosphine ligands were proposed by Kumada and Hayashi based on the pioneering work of Ugi, which was related to the synthesis of enantiomerically pure substituted metallocenes 1 related. These ligands are shown below: [0003] [0004] Ppfa as well as bppfa and bppfoh have been shown to be effective ligands for catalysts for various asymmetric transformations. From this starting po...

Claims

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Application Information

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IPC IPC(8): C07F9/48C07F17/02B01J31/00
CPCC07F17/02B01J31/1845B01J31/186B01J31/188B01J31/189B01J31/1895B01J31/2295B01J31/2404B01J31/2409B01J31/2452B01J31/2457B01J31/2495B01J2231/645B01J2531/0205B01J2531/82B01J2531/822B01J2531/842B01J2531/847B01J31/00C07F9/48C07F17/00
Inventor 陈卫平约翰·惠托尔
Owner SOLVIAS AG
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