Conformational Control in Dirhodium(II) Paddlewheel Catalysts Supported by Chalcogen-Bonding Interactions for Stereoselective Intramolecular C?H Insertion Reactions
Conformational Control in Dirhodium(II) Paddlewheel Catalysts Supported by Chalcogen-Bonding Interactions for Stereoselective Intramolecular C?H Insertion Reactions
复制标题
硫属键相互作用支持的铑 (II) 桨轮催化剂中立体选择性分子内 C?H 插入反应的构象控制
DOI：
10.1021/acscatal.0c03689
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发表时间：
2020
期刊：
影响因子：
12.9
通讯作者：
Furuta Takumi
中科院分区：
文献类型：
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作者：
Murai Takuya;Lu Wenjie;Kuribayashi Toshifumi;Morisaki Kazuhiro;Ueda Yoshihiro;Hamada Shohei;Kobayashi Yusuke;Sasamori Takahiro;Tokitoh Norihiro;Kawabata Takeo;Furuta Takumi
D2对称的双氮杂多酚δ-氨基酸衍生物是一种新型的含轴向手性联苯并硫杂环己烯-氨基酸衍生物的羧酸铋(II)催化剂。构象控制是通过每个配体中硫和氧原子之间的硫键相互作用来支持的，在催化活性Rh(II)中心周围提供了定义明确和均匀的不对称环境。这些结构性质使这类化合物成为不对称催化剂，用于立体选择性地将C-H插入到α-芳基-α-重氮乙酸酯中，生成各种顺式-α，β-二芳基γ-内酯，以及相应的反式异构体，具有高的非对映和对映选择性。利用这种构象可控催化剂，还完成了天然γ-内酯、肉桂内酯、肉桂菌素A7和肉桂内酯的短全合成。
D2-symmetric dirhodium(II) carboxylate catalysts that bear axially chiral binaphthothiophene δ-amino acid derivatives have been developed. Conformational control is supported through chalcogen-bonding interactions between sulfur and oxygen atoms in each ligand, providing well-defined and uniform asymmetric environments around the catalytically active Rh(II) centers. These structural properties make such complexes asymmetric catalysts for the stereoselective intramolecular C–H insertion into α-aryl-α-diazoacetates to yield a variety ofcis-α,β-diaryl γ-lactones, as well as the correspondingtrans-isomers through epimerization, in high diastereo- and enantioselectivities. Short total syntheses of the naturally occurring γ-lactones, cinnamomumolide, cinncassin A7, and cinnamomulactone were also accomplished using this conformationally controlled catalyst.