通过铑（II）催化的C-H插入过程实现新木脂素（-）-表-conocarpan和（+）-conocarpan的不对称合成以及（-）-表-conocarpan绝对构型的修正。
Asymmetric synthesis of neolignans (-)-epi-conocarpan and (+)-conocarpan via Rh(II)-catalyzed C-H insertion process and revision of the absolute configuration of (-)-epi-conocarpan.
作者信息
Natori Yoshihiro, Tsutsui Hideyuki, Sato Naoki, Nakamura Seiichi, Nambu Hisanori, Shiro Motoo, Hashimoto Shunichi
机构信息
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
出版信息
J Org Chem. 2009 Jun 5;74(11):4418-21. doi: 10.1021/jo900502d.
Abstract
Catalytic asymmetric synthesis of neolignan natural products (-)-epi-conocarpan and (+)-conocarpan has been achieved by exploiting an enantio- and diastereoselective intramolecular C-H insertion reaction to construct a cis-2-aryl-2,3-dihydrobenzofuran ring system as a key step. The C-H insertion reaction of 5-bromoaryldiazoacetate catalyzed by Rh(2)(S-PTTEA)(4), a new dirhodium(II) carboxylate complex that incorporates N-phthaloyl-(S)-triethylalaninate as chiral bridging ligands, provided 2-aryl-5-bromo-3-methoxycarbonyl-2,3-dihydrobenzofuran with exceptionally high diastereoselectivity (cis/trans = 97:3) and high enantioselectivity for the cis isomer (84% ee).
摘要
通过利用对映和非对映选择性分子内C-H插入反应构建顺式-2-芳基-2,3-二氢苯并呋喃环系统作为关键步骤，实现了新木脂素天然产物（-）-表松柏醇和（+）-松柏醇的催化不对称合成。由新型二铑（II）羧酸盐配合物Rh(2)(S-PTTEA)(4)催化的5-溴芳基重氮乙酸酯的C-H插入反应，该配合物包含N-邻苯二甲酰基-（S）-三乙丙氨酸作为手性桥连配体，以极高的非对映选择性（顺式/反式=97:3）和顺式异构体的高对映选择性（84% ee）提供了2-芳基-5-溴-3-甲氧基羰基-2,3-二氢苯并呋喃。
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Asymmetric synthesis of neolignans (-)-epi-conocarpan and (+)-conocarpan via Rh(II)-catalyzed C-H insertion process and revision of the absolute configuration of (-)-epi-conocarpan.通过铑（II）催化的C-H插入过程实现新木脂素（-）-表-conocarpan和（+）-conocarpan的不对称合成以及（-）-表-conocarpan绝对构型的修正。
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