A Double Deprotonation Strategy for Cascade Annulations of Palladium–Trimethylenemethanes and Morita–Baylis–Hillman Carbonates to Construct Bicyclohexane Frameworks

Here we report that the chemoselective activation of Tsuji's 2‐(cyanomethyl)allyl carbonates to generate the palladium–trimethylenemethane 1,3‐dipoles via a deprotonation strategy can be realized in the presence of Morita–Baylis–Hillman carbonates from substantial activated ketones. The followi...

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Published inAngewandte Chemie International Edition Vol. 60; no. 25; pp. 13913 - 13917
Main Authors Zhen‐Hong Yang, Chen, Peng, Zhi‐Chao Chen, Chen, Zhi, Du, Wei, Ying‐Chun Chen
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 01.06.2021
EditionInternational ed. in English
Subjects
Activated carbon
Aldehydes
Carbonates
Chemical reactions
Dipoles
Enantiomers
Hexanes
Ketones
Palladium
Substrates
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Summary:Here we report that the chemoselective activation of Tsuji's 2‐(cyanomethyl)allyl carbonates to generate the palladium–trimethylenemethane 1,3‐dipoles via a deprotonation strategy can be realized in the presence of Morita–Baylis–Hillman carbonates from substantial activated ketones. The following SN2′‐addition enables the formation of new 1,3‐dipole species having an activated alkene moiety through a second deprotonation process, which then undergo cascade [1+2]/[3+2] annulations to furnish complex bicyclic [3.1.0]hexane frameworks having three contiguous quaternary stereogenic centers with good to excellent enantioselectivity. Moreover, by using benzoyl aldehyde‐derived substrates, a [1+4]/[3+2] annulation sequence is similarly developed to produce fused cyclopenta[b]furan architectures.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202102842