Ligand-Controlled Regiodivergence in the Copper-Catalyzed [2,3]- and [1,2]-Rearrangements of Iodonium Ylides.
Despite the importance of allylic ylide rearrangements for the synthesis of complex molecules, the catalyst control of [2,3]- and [1,2]-rearrangements remains an unsolved problem. We developed the first regiodivergent [2,3]- and [1,2]-rearrangements of iodonium ylides that are controlled by copper catalysts bearing different ligands. In the presence of a 2,2'-dipyridyl ligand, diazoesters and allylic iodides react via a [2,3]-rearrangement pathway. Alternatively, a phosphine ligand favors the formation of the [1,2]-rearrangement product. A series of α-iodoesters containing a broad range of functional groups were obtained in high yields, regioselectivities, and diastereoselectivities. Deuterium-labeling studies suggest distinct mechanisms for the regioselective rearrangements.
Department of Biochemistry, The University of Texas Southwestern Medical Center at Dallas , 5323 Harry Hines Boulevard, Dallas, Texas 75390-9038, United States.
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B
Xu
Department of Biochemistry, The University of Texas Southwestern Medical Center at Dallas , 5323 Harry Hines Boulevard, Dallas, Texas 75390-9038, United States.
Uttam K
UK
Tambar
D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D007454:Iodides / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009861:Onium Compounds / Q000138:chemical synthesis*
D007454:Iodides; D008024:Ligands; D009861:Onium Compounds; D003300:Copper