TY - JOUR
T1 - Ligand-Controlled Regiodivergence in the Copper-Catalyzed [2,3]- and [1,2]-Rearrangements of Iodonium Ylides
AU - Xu, Bin
AU - Tambar, Uttam K.
N1 - Funding Information:
Financial support was provided by W. W. Caruth, Jr. Endowed Scholarship, Welch Foundation (I-1748), National Institutes of Health (R01GM102604), National Science Foundation (1150875), and Sloan Research Fellowship.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/9/21
Y1 - 2016/9/21
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.6b08624
DO - 10.1021/jacs.6b08624
M3 - Article
C2 - 27603216
AN - SCOPUS:84988599534
SN - 0002-7863
VL - 138
SP - 12073
EP - 12076
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 37
ER -