Syntheses and Applications of Optically Active Organoantimony (III) Compounds to Asymmetric Reaction.

光学活性有机锑(III)化合物的合成及其在不对称反应中的应用。

• 批准号: 09672172
• 负责人: KURITA Jyoji
• 金额: $ 2.11万
• 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: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09672172/
• 关键词: organoantimony compound; Sb-chiral compound; C2-chiral compound; optical resolution; chiral auxiliary; asymmetric reaction; 2, 2'-bis[diarylstibano]-1, 1'-binaphtyl; 7-aryldinaphtho[2, 1-b ; 1', 2'-d] stibole; パラジウム錯体; 不斉合成; dinaphtho[2,1-b;1',2

This study was performed to synthesize new Sb-chiral and C_2-symmetric optically active organoantimony (Sb) compounds and to clucidate their chemical propertics such as structural fcature, reactivity, and applicability as a chiral ligand to asymmetric syntheses.1. Syntheses and resolutions of Sb-chiral and C_2-symmetric optically active organoantimony (III) compounds : (a) The most straightforward method for the preparation of group 15 organometallic compounds is the nucleophilic displacement of the halogen group on appropriate metal halides (R_nMX_<3-n, > M=P.As.Sb.and Bi) by treatment with Grignard or organolithium reagents. However, this method has been proved to be unsatisfactory for the preparation of M-chiral compounds, because the halogen moiety on R_nMX_<3-n> is highly reactive as leaving groups. To solve this problem, we used ethynyl groups instead of halogen groups, and found a new general method for the preparation of Sb-Chiral organoantimony compounds by stepwise nucleophil … More ic displacement of tribromostibane via a bisethynyl stibane intermediate. (b) Althought, the atropisomeric 1, 1-naphthyl core is the parent framework of a steadily increasing family of C_2-symmetric chiral auxiliaries of high efficiency and a variety of phosphorous and arsenic compounds, such as BINAP, MOP, BINAs, and BINAPAs have been reported, no optically active bismuth analogues have been known. We demonstrated that the reaction of 2, 2'-dilithio-1, 1'-binaphthyl intermediate, prepared from 2, 2'-dibromo derivative by treatment with t-BuLi, with metal dihalides (ArSbBr_2, ArBiBr_2) afforded the corresponding binaphthyl dedivatives (BINASb and BINABi) which can be resolved by use of optically active Pd-complex as a resolving agent. Otherwise, treatment of the optically active 2, 2'-dilithio-1, 1'-binaphthyl intermediate with ArSbBr_2 resulted in ring closure to afford optically active 7-aryldinaphtho[2, 1-b, 1', 2'-d] stiboles which is the first isolated example of optically active dinaphthoheterols.2. Evaluation of optically active organoantimony (III) compounds for asvmmetric syntheses : Evaluation of the optically active organoantimony ligands obtained above for asymmetric reactions was made. The results show that the optically active organoantimony compounds were effective ligands for asymmetric reactions. such as transition metal catalyzed enantioselective reduction of prochiral ketones and asymmetric allylic substitution reaction of rac-1, 3-diphenyl-2-propenyl acetate with dimethyl malonate. Less

本研究合成了新的Sb-手性和c_2对称的光学活性有机锑（Sb）化合物，并阐明了它们的化学性质，如结构特征、反应性以及作为手性配体在不对称合成中的适用性。sb手性和c_2对称光学活性有机锑（III）化合物的合成和拆分：(a)制备第15族有机金属化合物最直接的方法是卤素基团在适当的金属卤化物（R_nMX_<3-n, > M=P.As.Sb）上的亲核位移。和Bi)用格氏试剂或有机锂试剂处理。然而，由于R_nMX_<3-n>上的卤素基团作为离去基具有很高的反应性，该方法已被证明对m -手性化合物的制备是不满意的。为了解决这一问题，我们用乙基代替卤素基，发现了一种新的通用方法，即通过亲核分子逐步取代二乙基二苯胺中间体取代三溴二苯胺来制备sb -手性有机锑化合物。(b)尽管已报道了稳定增长的高效c_2对称手性助剂家族和各种磷和砷化合物（如BINAP、MOP、BINAs和BINAPAs）的atrosom异构1,1 -naphthyl核的母体框架，但尚未发现具有光学活性的铋类似物。结果表明，由2,2 '-二溴衍生物经t-BuLi处理后，与金属二卤化物（ArSbBr_2, ArBiBr_2）反应得到相应的二溴衍生物（BINASb和BINABi），可以用光学活性pd配合物作为拆分剂进行拆分。另外，用ArSbBr_2处理具有旋光性的2,2′-二硫代- 1,1′-联萘基中间体，可形成具有旋光性的7-芳基二萘[2,1 -b, 1′，2′-d]杂酚，这是第一个分离到的具有旋光性的二萘杂酚。非对称合成中光学活性有机锑（III）化合物的评价：对上述非对称反应中获得的光学活性有机锑配体进行了评价。结果表明，光活性有机锑化合物是不对称反应的有效配体。如过渡金属催化的前手性酮的对映选择性还原和丙烯丙酯与丙二酸二甲酯的不对称烯丙基取代反应。少

项目成果

Tatsuhiro Tokunaga: "Direct dwtwction of intramolecular Sb-N nonbonded interaction by H^1-C^<13> and H^1-N^<15> heteronuclear multiple bond correlaticn specrscopy"Tetrahedron Lett.. 41. 1031-1034 (2000)

Tatsuhiro Tokunaga：“通过 H^1-C^<13> 和 H^1-N^<15> 异核多重键相关光谱直接分析分子内 Sb-N 非键相互作用”Tetrahedron Lett.. 41. 1031-1034 (2000

Naoki Kakusawa, Takashi Tsuchiya, Jyoji Kurita^*: "Photochemically induced coupling reaction of triarylstibines with olefines"Tetrahedron Lett.. 39. 9743-9746 (1998)

Naoki Kakusawa、Takashi Tsuchiya、Jyoji Kurita^*：“三芳基锑与烯烃的光化学诱导偶联反应”Tetrahedron Lett.. 39. 9743-9746 (1998)

Shuji Yasuike, Satoshi Tsukada, Jyoji Kurita^*, Takashi Tsuchiya: "Synthesis and structure of novel dibenzo [b. I] -1-oxa-6-heteroecines containing group 15 heavier elements."Heterocycles. 53. 525-528 (2000)

Shuji Yasuike、Satoshi Tsukada、Jyoji Kurita^*、Takashi Tsuchiya：“含有 15 族较重元素的新型二苯并 [b. I] -1-oxa-6-heteroecines 的合成和结构。”杂环。

Naiki Kakusawa: "Palladium-catalyzed cross -coupling reactions between 1 -alkynylstibines and acyl chlorides"Tetrahedron Lett.. 41. (2000)

Naiki Kakusawa：“1-炔基锑和酰氯之间的钯催化交叉偶联反应”Tetrahedron Lett.. 41. (2000)

Jyoji Kurita: "Resolution of racemic Sb-chiral stibindoles using an optically active ortho-palladated benzylamine derivative, via their diastereomeric complexes"Chem. Commun.. 191-192 (2000)

Jyoji Kurita：“使用光学活性邻位钯化苄胺衍生物通过其非对映体复合物解析外消旋 Sb-手性 stibindoles”Chem.