Clean Inversion of Configuration in the Pd-Catalyzed Cross-Coupling of 2-Bromo-1,3-dienes
- 17 October 2003
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (45) , 13636-13637
- https://doi.org/10.1021/ja0304392
Abstract
The Pd-catalyzed cross-coupling reaction of 2-bromo-1,3-dienes derived from alkyl aldehydes, especially with Cl2Pd(DPEphos) as a catalyst, proceeds with clean stereoinversion of the Br-bearing C=C bond to produce in high yields and in high stereoselectivity (>/=97-98%) conjugated Z,E dienes of potentially high utility in the synthesis of complex natural products. The observed stereoinversion cannot be readily accommodated by the widely accepted pi-sigma-pi rearrangement mechanism for isomerization of ordinary allylpalladium derivatives.Keywords
This publication has 18 references indexed in Scilit:
- Highly Selective Synthesis of (E)-3-Methyl-1-trialkylsilyl-3-en-1-ynes via trans-Selective Alkynylation Catalyzed by Cl2Pd(DPEphos) and Stereospecific Methylation with Methylzincs Catalyzed by Pd(tBu3P)2Organic Letters, 2003
- Highly Satisfactory Alkynylation of Alkenyl Halides via Pd-Catalyzed Cross-Coupling with Alkynylzincs and Its Critical Comparison with the Sonogashira AlkynylationOrganic Letters, 2003
- Asymmetric Total Synthesis of (−)-Callystatin A and (−)-20-epi-Callystatin A Employing Chemical and Biological MethodsChemistry – A European Journal, 2002
- A Highly Efficient, Selective, and General Method for the Synthesis of Conjugated (all-E)-Oligoenes of the (CHCH)n Type via Iterative Hydrozirconation−Palladium-Catalyzed Cross-CouplingOrganic Letters, 2002
- Total Synthesis of (−)-RatjadoneOrganic Letters, 2001
- Reactive D'esters α-Alleniques. Synthese regiospecifique de diesters γ-alleniques et de dienes−1,3.Published by Elsevier ,2001
- Studies on the Synthesis of Nargenicin A1: Highly Stereoselective Synthesis of the Complete Carbon Framework via the Transannular Diels−Alder Reaction of an 18-Membered MacrolideJournal of the American Chemical Society, 1996
- Antibiotics from Gliding Bacteria, LXIII. Ratjadone: A New Antifungal Metabolite from Sorangium cellulosumEuropean Journal of Organic Chemistry, 1995
- Stereoselective syntheses of di-, tri-, and tetrasubstituted enediynes from enynyl iodides via Pd-catalyzed coupling reactionsTetrahedron Letters, 1991
- A remarkable steric effect in palladium-catalyzed Grignard coupling: regio- and stereoselective monoalkylation and -arylation of 1,1-dichloro-1-alkenesJournal of the American Chemical Society, 1987