Asymmetric catalytic coupling of organoboranes, alkynes, and imines with a removable (trialkylsilyloxy)ethyl group-direct access to enantiomerically pure primary allylic amines
Asymmetric catalytic coupling of organoboranes, alkynes, and imines with a removable (trialkylsilyloxy)ethyl group-direct access to enantiomerically pure primary allylic amines
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DOI：
10.1002/anie.200460044
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发表时间：
2004-01-01
影响因子：
16.6
通讯作者：
Jamison, TF
中科院分区：
文献类型：
--
作者：
Patel, SJ;Jamison, TF
富含对映体的烯丙基胺经常被用作合成中间体、助剂和拆分剂，用于合成天然和非天然化合物。[1]本文报道了首次由炔烃、亚胺和有机硼烷催化合成烯丙基胺。在[Ni(CoD)2]衍生的络合物和手性二茂铁基膦的催化下，这个三组分过程在一次操作中提供了对映体富集烯丙基胺。亚胺氮上的(叔丁基二甲基硅氧基)乙基(TBSOCH2CH2)不仅使这些转化的反应性和选择性最大化，而且在偶合反应后很容易被除去，从而提供了直接获得多种伯烯丙基胺的途径，这些伯烯丙基胺可以重结晶到光学纯度。[2]已经报道了几种以高对映体选择性由炔和醛催化不对称合成烯丙醇的方法，[3]但尚未有从亚胺相应地合成烯丙胺的类似成功。5.Buchwald和他的同事已经报道，手性安莎-二茂锆亚胺络合物和炔类化合物的化学计量反应提供了高对映体过剩的三取代烯丙基胺。[6]双恶唑和(±)-司马汀促进有机锂试剂与亚胺的对映选择性加成(69-91%ee)；然而，在配体中催化的反应导致较低的选择性(51-82%ee)。[7]Hayashi和Ishigedani最近报道了一种互补的策略，涉及Ru催化的芳基锡烷与α，β不饱和亚胺的不对称加成反应。[8]我们最近报道了镍催化的炔烃、亚胺和有机硼试剂(硼酸和有机硼烷)的三组分偶联反应，该反应提供了
Enantiomerically enriched allylic amines are frequently used as synthetic intermediates, auxiliaries, and resolving agents in the synthesis of both natural and nonnatural compounds.[1] Herein we report the first highly enantioselective catalytic synthesis of allylic amines from alkynes, imines, and organoboranes. Catalyzed by a complex derived from [Ni (cod) 2] and a P-chiral ferrocenyl phosphane, this three-component process provides enantiomerically enriched, tetrasubstituted allylic amines in a single operation. A (tert-butyldimethylsilyloxy) ethyl (TBSOCH2CH2) group on the imine nitrogen not only maximizes reactivity and selectivity in these transformations, but also is easily removed after the coupling reaction, thus providing direct access to versatile primary allylic amines that can be recrystallized to optical purity.[2] Several catalytic asymmetric syntheses of allylic alcohols from alkynes and aldehydes in high enantioselectivities have been reported,[3] but comparable success has not been achieved for the corresponding synthesis of allylic amines from imines.[4, 5] Buchwald and co-workers have reported that stoichiometric reactions of chiral ansa-zirconocene imine complexes and alkynes provide trisubstituted allylic amines in high enantiomeric excess.[6] Bisoxazolines and (À)-sparteine promote enantioselective additions of organolithium reagents to imines (69–91% ee); however, reactions catalytic in the ligand result in lower selectivity (51–82% ee).[7] A complementary strategy was recently reported by Hayashi and Ishigedani involving the rhodium-catalyzed asymmetric addition of aryl stannanes to α, β-unsaturated imines.[8] We recently reported a nickel-catalyzed three-component coupling reaction of alkynes, imines, and organoboron reagents (boronic acids and organoboranes), which affords