Engaging Aldehydes in CuH‐Catalyzed Reductive Coupling Reactions: Stereoselective Allylation with Unactivated 1,3‐Diene Pronucleophiles
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nihms-1055953.pdf
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Accepted version
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966.14 KB
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Adobe PDF
Checksum (MD5)
9023d9046278ca65aa988a51617e8b79
Author(s)
Li, Chengxi
Shin, Kwangmin
Liu, Richard Y
Buchwald, Stephen L
Date Issued
2019
Journal
Angewandte Chemie - International Edition
Publisher
Wiley
Version
Author's final manuscript
Abstract
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Recently, CuH-catalyzed reductive coupling processes involving carbonyl compounds and imines have become attractive alternatives to traditional methods for stereoselective addition because of their ability to use readily accessible and stable olefins as surrogates for organometallic nucleophiles. However, the inability to use aldehydes, which usually reduce too rapidly in the presence of copper hydride complexes to be viable substrates, has been a major limitation. Shown here is that by exploiting relative concentration effects through kinetic control, this intrinsic reactivity can be inverted and the reductive coupling of 1,3-dienes with aldehydes achieved. Using this method, both aromatic and aliphatic aldehydes can be transformed into synthetically valuable homoallylic alcohols with high levels of diastereo- and enantioselectivities, and in the presence of many useful functional groups. Furthermore, using a combination of theoretical (DFT) and experimental methods, important mechanistic features of this reaction related to stereo- and chemoselectivities were uncovered.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1002/ANIE.201911008
