Davies Huw M L, Dai Xing, Long Matthew S
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260-3000, USA.
J Am Chem Soc. 2006 Feb 22;128(7):2485-90. doi: 10.1021/ja056877l.
The total synthesis of (-)-colombiasin A (2) and (-)-elisapterosin B (3) has been achieved. The key step is a C-H functionalization process, the combined C-H activation/Cope rearrangement, between methyl (E)-2-diazo-3-pentenoate and 1-methyl-1,2-dihydronaphthalenes. When the reaction is catalyzed by dirhodium tetrakis((R)-(N-dodecylbenzenesulfonyl)prolinate), Rh(2)(R-DOSP)(4), an enantiomer differentiation step occurs where one enantiomer of the dihydronaphthalene undergoes the combined C-H activation/Cope rearrangement while the other undergoes cyclopropanation. This sequence controls the three key stereocenters in the natural products such that the remainder of the synthesis is feasible using standard chemistry.
（-）-哥伦比亚菌素A（2）和（-）-埃利沙萜素B（3）的全合成已经实现。关键步骤是一个C-H官能化过程，即（E）-2-重氮-3-戊烯酸甲酯与1-甲基-1,2-二氢萘之间的C-H活化/Cope重排反应。当反应由四[（R）-（N-十二烷基苯磺酰基）脯氨酸根]二铑（Rh(2)(R-DOSP)(4)）催化时，会发生对映体分化步骤，其中二氢萘的一种对映体进行C-H活化/Cope重排反应，而另一种对映体发生环丙烷化反应。该序列控制了天然产物中的三个关键立体中心，使得使用标准化学方法进行其余的合成成为可能。
