甘氨酸衍生的二苯甲酮席夫碱在奎宁类手性相转移催化剂催化下与卤代物进行烷基化不对称合成手性α-氨基酸的{attr}3{attr}3228{/attr}8{/attr}。底物1（甘氨酸阴离子等价物）可以和卤代烃进行{attr}3131{/attr}。底物5（甘氨酸阳离子等价物）可以和烷基硼烷反应得到氨基酸。

反应机理

反应实例

tert-Butyl N-(diphenylmethylene)-4-fluoro-b-(4-fluorophenyl)-L-phenylalaninate (2). Schiff base 1(1.8 kg, 6.1 mol, prepared from benzophenone imine and t-butyl glycinate hydrochloride2) was added to 4,40-diflurorbenzhydryl bromide (1.2 equiv) in 1.8 L DCM followed by the cinchonidine-derived catalyst 4 (5 mol %) and the mixture was cooled to 0 ℃. Aq KOH (45% solution, 10 equiv) was added over 15–30 min at 0–5 ℃ and the two-phase mixture was stirred for 5 h. Workup of crude product (80:20 er) followed by recrystallization from EA:heptane afforded 1.72 kg of 3 (56%, >99% ee), mp 168–171 ℃.

【Org Process Res Dev., 2007, 11, 624】

tert-Butyl N-(diphenylmethylene)-2-acetoxyglycinate (5). Schiff base 1 (14.7 g, 0.05 mol) and lead tetraacetate (24.4 g, 0.055 mol) in DCM (150 mL) were stirred at r.t. for 5 h. Workup of the crude product followed by recrystallization from hexane afforded 16.2 g of 5 (92%), mp 105–106 ℃.

【J Am Chem Soc.， 1996， 118， 6070】

【Organic Letters, 2005, 7, 1129-1131】

【Tetrahedron Asymmetry, 2009, 20, 2600-2608】

相关文献

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7 O’Donnell MJ J Am Chem Soc 1996 118 6070

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15 Maruoka K Chem Rev 2007 107 5656

16 Patterson DE Org Process Res Dev 2007 11 624

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18 Scott WL Org Lett 2009 11 3558

编译自

一、Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, 207-208

二、APP: ReactionFlash