Rhodium‐Catalyzed Intermolecular trans‐Disilylation of Alkynones with Unactivated Disilanes,Angewandte Chemie International Edition

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Rhodium‐Catalyzed Intermolecular trans‐Disilylation of Alkynones with Unactivated Disilanes
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-07-19 , DOI: 10.1002/anie.201804223
Tao He ₁ , Li-Chuan Liu ₁ , Le Guo ₁ , Bin Li ₁ , Qing-Wei Zhang ₂ , Wei He ₁

Affiliation

Disilylation of alkynes could provide rapid entry to synthetically useful 1,2‐bissilyl‐alkenes, but is currently limited to activated disilanes reacting in an intramolecular fashion. Reported herein is an efficient rhodium(I)‐catalyzed intermolecular disilylation of a wide array of alkynones with unactivated disilanes. Importantly, this reaction produces exclusively trans‐disilylation products, selectivity that has been rarely reported. These disilylation products were transformed into interesting pentacyclic vinyl silane ethers, among other additional synthetic manipulations. Mechanistic studies uncovered that the unactivated disilanes underwent facile Si−Si activation and crossover under the reaction conditions.

中文翻译：

铑催化炔烃与未活化乙硅烷的分子间反二硅烷基化

炔烃的二甲硅烷基化可以快速进入合成上有用的1,2-双甲硅烷基-烯烃，但目前仅限于以分子内方式反应的活化乙硅烷。本文报道的是大量的炔烃与未活化的乙硅烷的高效铑（I）催化的分子间二烯化反应。重要的是，该反应仅产生反式二甲硅烷基化产物，其选择性鲜见报道。这些二甲硅烷基化产物被转化为令人感兴趣的五环乙烯基硅烷醚，以及其他附加的合成操作。机理研究发现，未反应的乙硅烷在反应条件下容易发生Si-Si活化和交叉反应。

更新日期：2018-07-19

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