Barlan Allan U, Micalizio Glenn C
Department of Chemistry, The Scripps Research Institute, Scripps Florida, Jupiter, FL 33458.
Tetrahedron. 2010 Jun 26;66(26):4775-4783. doi: 10.1016/j.tet.2010.02.062.
In investigations aimed at exploring the potential of disubstituted allenes in stereoselective synthesis, we report studies that explore the reductive cross-coupling reaction of vinylsilanes with a range of substituted allenes. Regiochemical control is attained by employing allenic alkoxides, where the proximal heteroatom dictates the site-selectivity in a process that proceeds by net formal metallo-[3,3] rearrangement (directed carbometalation/elimination). Stereoselectivity in these reactions is complex, with both the nature of allene substitution and relative stereochemistry of the substrate impacting the stereoselective generation of each alkene of a substituted 1,3-diene. 2009 Elsevier Ltd. All rights reserved.
在旨在探索二取代丙二烯在立体选择性合成中的潜力的研究中，我们报告了有关乙烯基硅烷与一系列取代丙二烯的还原交叉偶联反应的研究。通过使用丙二烯醇盐实现区域化学控制，其中近端杂原子在通过净形式金属-[3,3]重排（定向碳金属化/消除）进行的过程中决定位点选择性。这些反应中的立体选择性很复杂，丙二烯取代的性质和底物的相对立体化学都会影响取代的1,3-二烯的每个烯烃的立体选择性生成。2009爱思唯尔有限公司。保留所有权利。
