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Chiral bisphosphine ligand, its preparation method, intermediate and application

A reaction and compound technology, applied in the field of chiral bisphosphine ligands, can solve the problems of large amount of transition metal, low catalytic efficiency, low catalyst yield, etc.

Active Publication Date: 2021-02-09
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The technical problem to be solved by this invention is the technical problem that the catalyst yield of the enantioselective cyclization reaction of N-alkynone is low in the prior art, enantioselectivity is not high, catalytic efficiency is low or transition metal consumption is big, and then Provide a chiral bisphosphine ligand, its preparation method, intermediate and application

Method used

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  • Chiral bisphosphine ligand, its preparation method, intermediate and application
  • Chiral bisphosphine ligand, its preparation method, intermediate and application
  • Chiral bisphosphine ligand, its preparation method, intermediate and application

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Embodiment 1

[0152] The preparation of embodiment 1 (S, S)-DI-BI-DIME (L4)

[0153]

[0154] step 1

[0155]

[0156] To a solution of S1 (2.00 g, 8.84 mmol, 1.0 eq) and imidazole (1.20 g, 17.68 mmol, 2.0 eq) in dichloromethane (25 mL) under nitrogen at room temperature was added TBDPSCl (3.20 g, 11.49 mmol, 1.3 equiv). After stirring overnight at room temperature, the reaction was quenched with water, extracted with DCM, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. Purification of the residue by column chromatography (eluent: DCM / MeOH 100 / 1) afforded S2 as a white solid (4.11 g, 99%). S2: [α] D 25 =–8.2 (c=1.0, CHCl 3 ). 1 H NMR (500MHz, CDCl 3 )δ7.81(dd, J=7.7,1.5Hz,2H),7.81(dd,J=7.7,1.5Hz,2H),7.50–7.42(m,3H),7.39–7.35(m,1H),7.34 –7.29(m,2H),6.90(t,J=8.2Hz,1H),6.39(dd,J=8.2,1.8Hz,1H),6.02(dd,J=8.1,3.5Hz,1H),4.56( d, J=13.7Hz, 1H), 4.38(dd, J=13.2, 10.8Hz, 1H), 1.32(d, J=16.0Hz, 9H), 1.12(s, 9H); 13 C NMR (126MHz, CD...

Embodiment 2

[0177] The preparation of embodiment 2 chain N-alkynones

[0178]

[0179] step 1

[0180]

[0181] With tert-butyl toluenesulfonyl carbamate (17.7g, 65.3mmol, 1.0 equivalent) and K 2 CO 3 (13.5 g, 97.9 mmol, 1.5 equiv) was dissolved in 65 mL DMF and stirred at room temperature for 4 hours. Then (3-bromopropynylbenzene (14.0 g, 71.8 mmol, 1.1 equiv) was added to the above solution and stirred at room temperature for 10 hours. The reaction was quenched with water, extracted with EtOAc, washed with saturated brine, anhydrous Na 2 SO 4 Dry, filter, and concentrate under vacuum. Dissolve the residue in 60 mL DCM and 20 mL CF 3 COOH and stirred overnight at room temperature. Quenched with water, extracted with EtOAc, washed with saturated brine, anhydrous Na 2 SO 4 Dry, filter, and concentrate under vacuum. The residue was recrystallized from hexane / EtOAc to afford S9 as a white solid (17.5 g, 94%). S9: 1 H NMR (400MHz, CDCl 3 )δ7.85–7.78(m,2H),7.32–7.27(m,3H),7.2...

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Abstract

The invention discloses a chiral bisphosphine ligand, its preparation method, intermediate and application. The structure of the chiral bisphosphine ligand of the present invention is shown in formula I. Compared with the phosphine ligands in the prior art, the chiral bisphosphine ligands of the present invention are used for the enantioselective cyclization reaction of N-alkynones, achieving higher yields and better enantioselectivity or lower transition metal dosages.

Description

technical field [0001] The invention relates to a chiral bisphosphine ligand, its preparation method, intermediate and application. Background technique [0002] Transition-metal-catalyzed coupling of alkynes and acetylenes has become an effective method in current organic chemistry for the efficient construction of allyl alcohol derivatives. Recent developments in such reactions have greatly expanded their scope by using various transition metal catalysts, such as Ti, Ni, Rh, Ir, Ru, and Pd, as well as combinations of various coupling components and reducing or alkylating agents. and apply. Among them, the nickel-catalyzed coupling reactions of the π system pioneered by Mori, Montgomery, and Jamison are particularly attractive due to the wide substrate range and good functional group compatibility of the reactions developed by them. However, the enantioselective cyclization of these substrates, especially the enantioselective cyclization of chiral tertiary alcohols, has b...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/6574B01J31/24C07F7/18
CPCB01J31/2471B01J2231/641C07F7/188C07F9/657163Y02P20/55
Inventor 汤文军付文振刘国都
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI