Enantioselective Inverse Electron Demand (3 + 2) Cycloaddition of Palladium-Oxyallyl Enabled by a Hydrogen-Bond-Donating Ligand

Cycloaddition reactions between oxyallyl cations and alkenes are important transformations for the construction of ring systems. Although (4 + 3) cycloaddition reactions of oxyallyl cations are well-developed, (3 + 2) cycloadditions remain rare, and an asymmetric version has not yet been developed....

Full description

Saved in:
Bibliographic Details
Published inJournal of the American Chemical Society Vol. 143; no. 2; pp. 1038 - 1045
Main Authors Zheng, Yin, Qin, Tianzhu, Zi, Weiwei
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 20.01.2021
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
PAIRED CHIRAL LIGANDS
KETONES
CATALYSIS
DIRECT CONJUGATE ADDITION
1,3-DIENES
CONSTRUCTION
ALLYLATION
TRIMETHYLENEMETHANE
NONCOVALENT INTERACTIONS
CATIONS
Online AccessGet full text

Cover

More Information
Summary:Cycloaddition reactions between oxyallyl cations and alkenes are important transformations for the construction of ring systems. Although (4 + 3) cycloaddition reactions of oxyallyl cations are well-developed, (3 + 2) cycloadditions remain rare, and an asymmetric version has not yet been developed. Moreover, because oxyallyl cations are highly electrophilic, only electron-rich olefins can be used as cycloaddition partners. We herein report a method for enantioselective (3 + 2) cycloaddition reactions between palladium-oxyallyl species and electron-deficient nitroalkenes. This transformation was enabled by a rationally designed hydrogen-bond-donating ligand (FeUrPhos) and proceeded via an inverse electron demand pathway. Using this method, we could assemble cyclopentanones with up to three contiguous stereocenters with high enantioselectivity and good to excellent diastereoselectivity.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.0c11504