TY - JOUR
T1 - Dynamic Kinetic Resolution of Allylic Azides via Asymmetric Dihydroxylation
AU - Ott, Amy A.
AU - Goshey, Charles S.
AU - Topczewski, Joseph J.
PY - 2017/6/14
Y1 - 2017/6/14
N2 - The catalytic enantioselective preparation of densely functionalized amines is a fundamental synthetic challenge. To address this challenge, we report for the first time that the Winstein rearrangement can be enlisted as the racemization pathway in a dynamic kinetic resolution of allylic azides. Alkene functionalization by Sharpless dihydroxylation affords tertiary azides in excellent enantioselectivity (up to 99:1 er). This approach establishes the chirality of the tertiary azide, obviates the need to directly forge either a congested C-N or C-C bond at the new nitrogenous stereocenter, and establishes additional functionality. Several examples demonstrate further elaboration of this functionality.
AB - The catalytic enantioselective preparation of densely functionalized amines is a fundamental synthetic challenge. To address this challenge, we report for the first time that the Winstein rearrangement can be enlisted as the racemization pathway in a dynamic kinetic resolution of allylic azides. Alkene functionalization by Sharpless dihydroxylation affords tertiary azides in excellent enantioselectivity (up to 99:1 er). This approach establishes the chirality of the tertiary azide, obviates the need to directly forge either a congested C-N or C-C bond at the new nitrogenous stereocenter, and establishes additional functionality. Several examples demonstrate further elaboration of this functionality.
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U2 - 10.1021/jacs.7b04203
DO - 10.1021/jacs.7b04203
M3 - Article
C2 - 28574252
AN - SCOPUS:85020542115
SN - 0002-7863
VL - 139
SP - 7737
EP - 7740
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 23
ER -