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.
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 R(1)M (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 (>or=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.
Negishi
Ei-Ichi
E
Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084, USA. negishi@purdue.edu
Wang
Guangwei
G
Rao
Honghua
H
Xu
Zhaoqing
Z
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D055772:Green Chemistry Technology / Q000379:methods*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D000480:Alkynes; D009942:Organometallic Compounds; D010165:Palladium
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