Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
J Am Chem Soc. 2011 Jun 29;133(25):9716-9. doi: 10.1021/ja2039248. Epub 2011 Jun 7.
The Pd-catalyzed cross-coupling of racemic tertiary allylic carbonates and allylboronates is described. This reaction generates all-carbon quaternary centers in a highly regioselective and enantioselective fashion. The outcome of these reactions is consistent with a process that proceeds by way of 3,3'-reductive elimination of bis(η(1)-allyl)palladium intermediates. Strategies for distinguishing the product alkenes and application to the synthesis of (+)-α-cuparenone are also described.
手性三级烯丙基碳酸酯和烯丙基硼酸酯的钯催化交叉偶联反应被描述。该反应以高度区域选择性和对映选择性的方式生成全碳季碳中心。这些反应的结果与通过双（η(1)-烯丙基）钯中间体的 3,3'-还原消除过程一致。还描述了区分产物烯烃的策略及其在(+)-α-古巴烯酮合成中的应用。
