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Synthesis of Optically Active Orgnoantimony Compounds and Their Application for Asymmetric Reactions

光学活性有机锑化合物的合成及其在不对称反应中的应用

基本信息

批准号：
13672242
负责人：
KURITA Jyoji
金额：
$ 2.18万
依托单位：
Hokuriku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

Transition metal-catalyzed asymmetric reactions with enantiopure ligands have been of much interest for synthetic chemists because of their wide applicability in the synthesis of a variety of biologically active compounds. Despite remarkable usefulness as a chiral inducer of phosphorous and arsenic ligands in asymmetric synthesis, however, asymmetric reactions with optically active organoantimony ligands have not been reported so far due to the limited access to this class of compounds. In these points of view, we planed to establish a versatile route for the synthesis of optically active organoantimony compounds and to investigate their potential for chiral inducer in asymmetric reactions.1.Synthesis of Optically Active C_2-Chiral Organoantimony Compounds and Their Use for Asymmetric ReactionsRacemic C_2-Symmetrical 2,2'-diarylstibano-1,1'-binaphthyl (BINASb:1), C_2-unymmetrical 2-diarylstibano-2'-dipheny phosphano-1,1'-binaphthyl (BINAPSb:2), 2-diarylstibano-2'-dimethylamino-1,1'-bin … More aphthyl (MASb:3) has been prepared from (±)-2,2'-dibromo-1,1'-binaphthyl and they could be successfully resolved in enantiopure form via separation of diastereomeric mixture of the Pd-complex arose from the reaction with optically active palladium reagent such as di-μ-chlorobis{(S)-2-[1-(dimethylamino)ethyl]phenyl-C^1,N}dipalladium(II). Research on several asymmetric reactions, such as asymmetric reduction of prochiral ketones (Reaction 1), allylic alkylation of allyl acetate (Reaction 2), and hydrosilylation of styrene (Reaction 3) by use of these organoantimony ligands as chiral auxiliaries revealed that BINASb (1) was a useful ligand for the Reaction 2 and BINAPSb (2) had high potential for the reaction 3. In the latter reaction, BINAPSb (2) should function as bidentate ligand at the early stage of the reaction and as monodentate ligand at the last stage.2.Synthesis of Optically Active C-Chiral and Sb-Chiral Organoantimony Compounds Bearing Benzylamine and Oxazoline Moieties and Their Use for Asymmetric ReactionsThe title compounds, C-chiral (S)-(α-methyl-2-di-p-tolylstibanobenzyl)dimethylamine (AMSb:4) and its chromium complex (AMSb-Cr:5), and C- and Sb-chiral Sb(R/S)-(aryl)[2-(S)-(1-dimethylaminoethyl)phenyl](p-Tolyl)stibane (6) has been synthesized from common (S)-(α-methylbenzyl)dimethylamine. Similar synthetic route could be applied to the synthesis of C(S),Sb(R/S)-aryl[2-(2-oxazolino)phenyl](p-tolyl)stibane (7) from (S)-4-isopropyl-2-phenyl-2-oxazoline. The asymmetric reactions by use of these ligands showed that the compound 7 was effective for the Reaction 2, although the other ligands (4〜6) had modest ability as chiral auxiliary for these asymmetric reactions. Less

过渡金属催化的对映体纯配体的不对称反应因其在合成各种生物活性化合物中的广泛适用性而引起了合成化学家的极大兴趣。尽管在不对称合成中作为磷和砷配体的手性诱导剂具有显着的用途，然而，由于此类化合物的获取有限，迄今为止尚未报道与光学活性有机锑配体的不对称反应。鉴于这些观点，我们计划建立一种合成光学活性有机锑化合物的通用路线，并研究其在不对称反应中作为手性诱导剂的潜力。1.光学活性C_2-手性有机锑化合物的合成及其在不对称反应中的应用外消旋C_2-对称 2,2'-二芳基斯蒂班基-1,1'-联萘基 (BINASb:1)、C_2-不对称 2-二芳基斯蒂班基-2'-二苯基膦基-1,1'-联萘基 (BINAPSb:2)、2-二芳基斯蒂班基-2'-二甲基氨基-1,1'-bin … 更多 aphthyl (MASb:3) 已由以下物质制备 (±)-2,2'-二溴-1,1'-联萘，通过分离与光学活性钯试剂反应产生的钯配合物的非对映体混合物，可以成功地将它们解析为对映体纯形式二-μ-氯双{(S)-2-[1-(二甲基氨基)乙基]苯基-C^1,N}二钯(II)。对几个不对称反应的研究，例如使用这些有机锑配体作为手性助剂的前手性酮的不对称还原（反应 1）、乙酸烯丙酯的烯丙基烷基化（反应 2）和苯乙烯的氢化硅烷化（反应 3）表明，BINASb (1) 是反应 2 的有用配体，BINAPSb (2) 具有很高的潜力反应 3. 在后一个反应中，BINAPSb (2) 应在反应的早期阶段充当二齿配体，并在最后阶段充当单齿配体。2. 带有苯甲胺和恶唑啉部分的光学活性 C-手性和 Sb-手性有机锑化合物的合成及其在不对称反应中的用途标题化合物，C-手性 (S)-(α-甲基-2-二-对甲苯基斯蒂苯甲基)二甲胺 (AMSb:4) 及其铬配合物 (AMSb-Cr:5)，以及 C- 和 Sb-手性 Sb(R/S)-(芳基)[2-(S)-(1-二甲基氨基乙基)苯基](对甲苯基)锑烷 (6) 由常见物质合成 (S)-(α-甲基苄基)二甲胺。类似的合成路线可以应用于从(S)-4-异丙基-2-苯基-2-恶唑啉合成C(S),Sb(R/S)-芳基[2-(2-恶唑啉基)苯基](对甲苯基)锑烷(7)。使用这些配体的不对称反应表明，化合物7对于反应2是有效的，尽管其他配体(4〜6)作为这些不对称反应的手性助剂的能力有限。较少的