Regio- and diastereoselective rhodium-catalyzed allylic substitution with acyclic alpha-alkoxy-substituted copper(I) enolates: stereodivergent approach to 2,3,6-trisubstituted dihydropyrans

Journal of the American Chemical Society
P Andrew Evans, Michael J Lawler

Abstract

The regio- and diastereoselective transition metal-catalyzed allylic alkylation using alpha-heteroatom-substituted ketones and carboxylic acid derivatives represents a challenging and important synthetic transformation. We have developed a regio- and diastereoselective rhodium-catalyzed allylic alkylation reaction utilizing the copper(I) enolates derived from alkyl protected acyclic alpha-alkoxy aryl ketones. This study suggests that the ability to form a chelated enolate intermediate is crucial for obtaining high diastereoselectivity, whereas excellent regioselectivity is obtained regardless of the substituent. Hence, the excellent selectivity coupled with the synthetic utility of alpha-alkoxy aryl ketone enolates makes this an important new method for the construction of acyclic adjacent ternary stereogenic centers. Finally, the synthetic utility of this protocol was highlighted through the conversion of the aryl ketone to the ester and the development of a stereodivergent approach to 2,3,6-trisubstituted dihydropyrans relevant to target-directed synthesis.

References

Apr 13, 2000·Angewandte Chemie·U Kazmaier, F L Zumpe
Jun 20, 2002·Journal of the American Chemical Society·Barry M Trost, Kalindi Dogra

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Citations

Mar 30, 2011·Journal of the American Chemical Society·Dong LiMasaya Sawamura
Dec 25, 2009·Journal of the American Chemical Society·Hirohisa OhmiyaMasaya Sawamura
Jun 2, 2005·Chemical Communications : Chem Comm·Erin C Burger, Jon A Tunge
Aug 23, 2016·Journal of the American Chemical Society·Xiaohong HuoWanbin Zhang
Sep 22, 2020·ChemistryOpen·Lukas Junk, Uli Kazmaier
Oct 3, 2015·Angewandte Chemie·Tobias SandmeierErick M Carreira
Nov 20, 2012·Chemical Communications : Chem Comm·John M KetchamAaron Aponick
Jul 27, 2021·Chemical Reviews·Timothy B Wright, P Andrew Evans
Aug 23, 2019·Organic Letters·Shaukat AliCongyang Wang
Sep 16, 2017·Chemical Reviews·You Yang, Biao Yu
May 11, 2013·Journal of the American Chemical Society·Genping HuangFahmi Himo
May 26, 2018·Journal of the American Chemical Society·Sheng-Biao TangShu-Li You

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