TY - JOUR
T1 - Carbonylative, Catalytic Deoxygenation of 2,3-Disubstituted Epoxides with Inversion of Stereochemistry
T2 - An Alternative Alkene Isomerization Method
AU - Lamb, Jessica R.
AU - Hubbell, Aran K.
AU - MacMillan, Samantha N.
AU - Coates, Geoffrey W.
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/4/29
Y1 - 2020/4/29
N2 - Reactions facilitating inversion of alkene stereochemistry are rare, sought-after transformations in the field of modern organic synthesis. Although a number of isomerization reactions exist, most methods require specific, highly activated substrates to achieve appreciable conversion without side product formation. Motivated by stereoinvertive epoxide carbonylation reactions, we developed a two-step epoxidation/deoxygenation process that results in overall inversion of alkene stereochemistry. Unlike most deoxygenation systems, carbon monoxide was used as the terminal reductant, preventing difficult postreaction separations, given the gaseous nature of the resulting carbon dioxide byproduct. Various alkyl-substituted cis- A nd trans-epoxides can be reduced to trans- A nd cis-alkenes, respectively, in >99:1 stereospecificity and up to 95% yield, providing an alternative to traditional, direct isomerization approaches.
AB - Reactions facilitating inversion of alkene stereochemistry are rare, sought-after transformations in the field of modern organic synthesis. Although a number of isomerization reactions exist, most methods require specific, highly activated substrates to achieve appreciable conversion without side product formation. Motivated by stereoinvertive epoxide carbonylation reactions, we developed a two-step epoxidation/deoxygenation process that results in overall inversion of alkene stereochemistry. Unlike most deoxygenation systems, carbon monoxide was used as the terminal reductant, preventing difficult postreaction separations, given the gaseous nature of the resulting carbon dioxide byproduct. Various alkyl-substituted cis- A nd trans-epoxides can be reduced to trans- A nd cis-alkenes, respectively, in >99:1 stereospecificity and up to 95% yield, providing an alternative to traditional, direct isomerization approaches.
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U2 - 10.1021/jacs.0c02653
DO - 10.1021/jacs.0c02653
M3 - Article
C2 - 32309937
AN - SCOPUS:85083881336
SN - 0002-7863
VL - 142
SP - 8029
EP - 8035
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 17
ER -