通过金催化的掩蔽卡宾与亚乙烯基的交叉偶联生成丙二烯。
Allene formation by gold catalyzed cross-coupling of masked carbenes and vinylidenes.
作者信息
Lavallo Vincent, Frey Guido D, Kousar Shazia, Donnadieu Bruno, Bertrand Guy
机构信息
University of California Riverside-Centre National de la Recherche Scientifique Joint Research Chemistry Laboratory (Unité Mixte Internationale 2957), Department of Chemistry, University of California, Riverside, CA 92521-0403, USA.
出版信息
Proc Natl Acad Sci U S A. 2007 Aug 21;104(34):13569-73. doi: 10.1073/pnas.0705809104. Epub 2007 Aug 13.
Abstract
Addition of a sterically demanding cyclic (alkyl)(amino)carbene (CAAC) to AuCl(SMe(2)) followed by treatment with Et(3)Si(Tol)B(C(6)F(5))(4) in toluene affords the isolable (CAAC)Au(eta(2)-toluene)B(C(6)F(5))(4) complex. This cationic Au(I) complex efficiently mediates the catalytic coupling of enamines and terminal alkynes to yield allenes and not propargyl amines as observed with other catalysts. Mono-, di-, and tri-substituted enamines can be used, as well as aryl-, alkyl-, and trimethylsilyl-substituted terminal alkynes. The reaction tolerates sterically hindered substrates and is diastereoselective. This general catalytic protocol directly couples two unsaturated carbon centers to form the three-carbon allenic core. The reaction most probably proceeds through an unprecedented "carbene/vinylidene cross-coupling."
摘要
在甲苯中，将空间位阻较大的环状（烷基）（氨基）卡宾（CAAC）添加到AuCl(SMe₂)中，然后用[Et₃Si(Tol)]⁺[B(C₆F₅)₄]⁻处理，得到可分离的[(CAAC)Au(η²-甲苯)]⁺[B(C₆F₅)₄]⁻配合物。与其他催化剂所观察到的情况不同，这种阳离子Au(I)配合物能有效地介导烯胺与末端炔烃的催化偶联，生成丙二烯而非炔丙基胺。单取代、二取代和三取代的烯胺以及芳基、烷基和三甲基硅基取代的末端炔烃均可使用。该反应能够耐受空间位阻较大的底物，并且具有非对映选择性。这种通用的催化方法直接将两个不饱和碳中心偶联，形成三碳丙二烯核心。该反应很可能通过一种前所未有的“卡宾/亚乙烯基交叉偶联”进行。
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