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Quantitative Analyses and Control of Catalytic Organic Transformations

催化有机转化的定量分析和控制

基本信息

批准号：
14078212
负责人：
KITAMURA Masato
金额：
$ 15.62万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

Asymmetric hydrogenation of a-(acylamino)acrylic esters with Ru(CH_3COO)_2 [(S)-binap] (BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) has been revealed to proceed via monohydride-unsaturate mechanism. The enantioselectivity that is opposite to the (S)-BINANP-Rh case has been interpreted in terms of stereo-complementary models of the enamide/metal chelate complexes. The detailed analysis of the isotopomer ratios has proved that the major S and minor R enantiomers are produced via the same mechanism involving diastereomeric intermediates. With (Z)-3-phenyl-2-butenoic acid, however, the minor enantiomer is formed mostly by mechanisms that differ from the major one. The observed enantioselectivity has generally been interpreted to result from competing diastereomorphic catalytic cycles caused by a single chiral catalyst; however, this supposition has not been substantiated. Our study calls into question such a generalized treatment. Furthermore, in this research project, we have found two new catalyses 1. Cp^*Rh(III)-catalyzed Leuckart-Wallach (LW)-type reductive amination of ketones and 2. catalytic allyl ether cleavage and formation using [CpRu(CH_3CN)_3]PF_6 and 2-pyridinecarboxylic acid derivatives. Both process are very clean and operational simple. In particular, the new salt waste-free allyl ether synthesis has overcome the long-pending problems in Williamson's ether synthesis.

本文报道了Ru（CH_3COO）_2 [（S）-binap]（BINAP = 2，2 ′-双（二苯基膦基）-1，1 ′-联萘）催化α-（酰氨基）丙烯酸酯的不对称氢化反应。与（S）-BINANP-Rh情况相反的对映体选择性已被解释为烯酰胺/金属螯合物的立体互补模型。同位素异构体比率的详细分析已经证明，主要的S和次要的R对映异构体通过涉及非对映异构体中间体的相同机制产生。然而，对于（Z）-3-苯基-2-丁烯酸，次要对映体主要通过与主要对映体不同的机制形成。观察到的对映体选择性通常被解释为由单一手性催化剂引起的竞争性非对映体催化循环的结果;然而，这种假设尚未得到证实。我们的研究对这种普遍的治疗提出了质疑。此外，在本研究项目中，我们发现了两种新的催化剂1。Cp^*Rh（III）催化的Leuckart-Wallach（LW）型酮和2的还原胺化。用[CpRu（CH_3CN）_3]PF_6和2-吡啶羧酸衍生物催化烯丙基醚的裂解和生成。这两个过程都非常干净，操作简单。特别是新的无盐废烯丙基醚合成法，克服了威廉姆森的醚合成法长期悬而未决的问题。