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Alpha-menaphthyl substituted spiro bis(oxazoline) ligands, synthetic method and application thereof in synthesizing pyrazolidine derivatives

A technology of bisoxazoline and spiro ring, which is applied in the field of synthesis of spiro bisoxazoline ligands, can solve limited problems, achieve strong regulation ability, high catalytic activity and chiral induction effect, and simple synthesis method Effect

Active Publication Date: 2009-10-21
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

However, the methods for synthesizing optically active pyrazolidines with high enantioselectivity are very limited.

Method used

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  • Alpha-menaphthyl substituted spiro bis(oxazoline) ligands, synthetic method and application thereof in synthesizing pyrazolidine derivatives
  • Alpha-menaphthyl substituted spiro bis(oxazoline) ligands, synthetic method and application thereof in synthesizing pyrazolidine derivatives
  • Alpha-menaphthyl substituted spiro bis(oxazoline) ligands, synthetic method and application thereof in synthesizing pyrazolidine derivatives

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031]

[0032] Under inert gas protection, add 308mg (R a )-1, 442mg aminoalcohol, 869mg DCC and 297mg nitrogen hydroxybenzotriazole. Add 40 mL of tetrahydrofuran under ice-cooling, keep at 0°C for 1-10 hours, then naturally rise to room temperature, react overnight, and TLC detects that the reaction is complete (petroleum ether: ethyl acetate = 1:1). The solvent was removed under reduced pressure, and the product was directly used in the next reaction by short column filtration.

[0033] Add 13 mg of DMAP to the reaction tube containing the product obtained in the previous step. After ventilating, add 30 mL of dichloromethane, add 0.68 mL of triethylamine under ice bath, add 0.34 mL of methanesulfonyl chloride after stirring for a while, and keep the reaction at 0°C After 0.5-5 hours, add 2.9 mL of triethylamine, let it rise to room temperature naturally, and react overnight, and TLC detects that the reaction is complete. Add 100mL ether to the system for extraction, th...

Embodiment 2

[0036] (R 1 =Bn,R 2 =Bn,R 3 =Ph)

[0037] Pd(dba) 2 (3mg, 0.0053mmol) and (R a , S, S)-3 (4mg, 0.0063mmol) (ligand synthesized in Example 1) was complexed in 1mL tetrahydrofuran for 0.5-3 hours, then added Ag 3 PO 4 (19mg, 0.045mmol), 4a (64mg, 0.10mmol), iodobenzene 5a (25mg, 0.12mmol) and 1mL tetrahydrofuran. The reaction was reacted at 0-200°C, TLC followed the end of the reaction, and directly spin-dried column chromatography yielded no Viscous liquid 61 mg (R)-6aa (85% yield, 93% ee). 1 H NMR (400MHz, CDCl 3 ): δ7.28-7.06(m, 21H), 7.05-6.98(m, 4H), 5.55(s, 1H), 5.44-5.38(m, 1H), 5.13-4.78(m, 9H), 3.00(dd , J=13.2, 8.4Hz, 1H), 2.47(dd, J=13.2, 2.8Hz, 1H); 13 C NMR (100.5MHz, CDCl 3 ): δ167.8, 166.0, 157.0, 153.3, 143.6, 138.4, 135.5, 135.3, 134.9, 134.4, 128.40, 128.36, 128.2, 128.15, 128.12, 128.07, 128.0, 127.8, 71.5, 127.6, 123.6 68.3, 68.2, 68.0, 61.3, 41.3; MS (ESI): m / z 749 (M+K + ), 733 (M+Na + ); IR (neat): 1738, 1586, 1498, 1455, 1397, 1337, 1276, 118...

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Abstract

The invention provides spiro bis(oxazoline) ligands with a plurality of chiral centers, a preparation method and application. The ligands are provided with axial chirality of a spiro backbone and central chirality of an oxazoline ring. The ligands can be prepared by condensation of chiral spiro diacid and corresponding alkamine. The invention also provides application of the spiro bis(oxazoline) ligands in synthesizing pyrazolidine derivatives in high regioselectivity and high enantioselectivity.

Description

technical field [0001] The present invention relates to a class of chiral ligands, a synthesis method and its use, that is, the synthesis and use of a spirocyclic bisoxazoline ligand with multiple chiral centers. At the same time, the patent provides a method for using the ligand to synthesize pyrazolidine derivatives with high regioselectivity and high enantioselectivity. Background technique [0002] Chiral bisoxazoline ligands are a class of important chiral ligands. Since G.Helmchen first disclosed the synthesis of bisoxazoline ligands (BOX) in Tetrahderon, 1993,34,1769,3149, the Ligands have been widely used in a variety of asymmetric reactions. Although their ligands have good yields and enantioselectivities in allylic amination and allylic alkylation reactions, their application in asymmetric reactions involving allenes is not ideal. (J. Org. Chem. 1999, 64, 7312). Therefore, finding new chiral ligands to adapt to some reactions or more reactions and have high cata...

Claims

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Application Information

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IPC IPC(8): C07D263/12B01J31/22C07B53/00C07B37/02C07B37/10C07D231/04C07D405/06C07D409/06
Inventor 麻生明舒伟
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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