Alkyne Elementometalation-Pd-Catalyzed Cross-Coupling. Toward Synthesis of All Conceivable Types of Acyclic Alkenes in High Yields, Efficiently, Selectively, Economically, and Safely: "Green" Way

作者：Negishi Ei ichi^*; Wang Guangwei; Rao Honghua; Xu Zhaoqing

来源：Journal of Organic Chemistry, 2010, 75(10): 3151-3182.

DOI：10.1021/jo1003218

Palladium-catalyzed cross-coupling reactions, especially those involving Zn, Al, Zr (Negishi coupling), and B (Suzuki coupling), collectively have brought about "revolutionary" changes in organic synthesis. Thus, two regio- and stereodefined carbon groups generated as RIM (M = Zn, Al, B, Cu, Zr, etc.) and R(2)X (X = I, Br, OTs, etc.) may now be cross-coupled to give R(1)-R(2) with essentially full retention of all structural features. For alkene syntheses, alkyne elementometalation reactions including hydrometalation (B, Al, Zr, etc.), carbometalation (Cu, Al Zr, etc.), and haloboration (BX(3) where X is Cl, Br, and I) have proven to be critically important. Some representative examples of highly efficient and selective (>= 98%) syntheses of di-, tri-, and oligoenes containing regio- and stereodefined di- and trisubstituted alkenes of all conceivable types will be discussed with emphasis on those of natural products. Some interesting but undesirable cases involving loss of the initial structural identities of the alkenyl groups are attributable to the formation of allylpalladium species, which must be either tamed or avoided. Some such examples involving the synthesis of 1,3-, 1,4-, and 1,5-dienes will also be discussed.

• 出版日期2010-5-21