Gold(I)-Catalyzed Desymmetrization of 1,4-Dienes by an Enantioselective Tandem Alkoxylation/Claisen Rearrangement.
Gold(I)-Catalyzed Desymmetrization of 1,4-Dienes by an Enantioselective Tandem Alkoxylation/Claisen Rearrangement.
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DOI：
10.1002/anie.201503357
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发表时间：
2015-07-13
期刊：
影响因子：
--
通讯作者：
Toste FD
中科院分区：
文献类型：
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作者：
Wu H;Zi W;Li G;Lu H;Toste FD
在 (S)-DTBM-Segphos(AuCl)2/AgBF4 催化下，通过 1,4-二烯的策略去对称化实现了对映选择性烷氧基化/克莱森重排反应。该反应体系对3,3-重排产物的形成具有高度选择性，以良好的收率和良好至优异的对映选择性提供具有各种取代基的环庚烯。这种转化进一步扩展到双环底物，为轻松组装 5,6-和 6,7-稠环系统提供了机会。
An enantioselective alkoxylation/Claisen rearrangement reaction was achieved by a strategic desymmetrization of 1,4-dienes under the catalysis of (S)-DTBM-Segphos(AuCl)2/AgBF4. This reaction system was highly selective for the formation of 3,3-rearrangement products, providing cycloheptenes with various substitutions in good yield and good to excellent enantioselectivity. This transformation was further extended to bicyclic ring substrates, providing the opportunity to easily assemble 5,6- and 6,7-fused ring systems.