Mechanistic analysis of gold(I)-catalyzed intramolecular allene hydroalkoxylation reveals an off-cycle bis(gold) vinyl species and reversible C-O bond formation.

Mechanistic analysis of gold(I)-catalyzed intramolecular allene hydroalkoxylation reveals an off-cycle bis(gold) vinyl species and reversible C-O bond formation.
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DOI:
10.1021/ja303844h
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发表时间:
2012-06-06
影响因子:
15
通讯作者:
Widenhoefer, Ross A.
Widenhoefer, Ross A.
中科院分区:
化学1区
文献类型:
--
作者:
Brown, Timothy J.;Weber, Dieter;Gagne, Michel R.;Widenhoefer, Ross A.

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金(I)催化的分子内丙二烯加氢烷氧基化的机理研究建立了一种机制,涉及快速可逆的C-O键形成,然后是单(金)乙烯基配合物的周转限制原脱气。这种循环途径与催化剂聚集和非循环双(金)乙烯基络合物的形成竞争。
Mechanistic investigation of gold(I)-catalyzed intramolecular allene hydroalkoxylation established a mechanism involving rapid and reversible C–O bond formation followed by turnover-limiting protodeauration from a mono(gold) vinyl complex. This on-cycle pathway competes with catalyst aggregation and formation of an off-cycle bis(gold) vinyl complex.
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