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. 2022 Sep 14;144(36):16298-16302.
doi: 10.1021/jacs.2c07394. Epub 2022 Aug 30.

Borylated Cyclopropanes as Spring-Loaded Entities: Access to Vicinal Tertiary and Quaternary Carbon Stereocenters in Acyclic Systems

André U Augustin  1 , Sergio Di Silvio  1 , Ilan Marek  1
Affiliations

Borylated Cyclopropanes as Spring-Loaded Entities: Access to Vicinal Tertiary and Quaternary Carbon Stereocenters in Acyclic Systems

André U Augustin et al. J Am Chem Soc. .

Abstract

Herein, we present the formation of acyclic frameworks bearing two consecutive stereocenters of either tertiary or quaternary nature starting from easily accessible cyclopropenes. This holistic approach involves a regio- and diastereoselective hydro- or carboborylation of substituted cyclopropenyl esters. Formation of boronate complexes of the latter via the addition of nucleophiles and subsequent stereospecific 1,2-migration with carbon-carbon bond cleavage delivered the title compounds.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Stereoselective Synthesis of Acyclic Compounds Bearing Vicinal Stereocenters
Scheme 2
Scheme 2. Cu-Catalyzed Hydro- and Carboborylation of Substituted Cyclopropenyl Esters
Scheme 3
Scheme 3. Sequence of Reduction–Phosphorylation
Scheme 4
Scheme 4. 1,2-Metalate Rearrangement of Cyclopropyl Boronic Esters
See this image and copyright information in PMC

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