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Construction of Seven-Membered Oxacycles Using a Rh(I)-Catalyzed Cascade C-C Formation/Cleavage of Cyclobutenol Derivatives

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Title
Construction of Seven-Membered Oxacycles Using a Rh(I)-Catalyzed Cascade C-C Formation/Cleavage of Cyclobutenol Derivatives
Author(s)
Ham, Jin Su; Mina Son; Na, Christina G.; Bohyun Park; Mu-Hyun Baik; Sarpong, Richmond
Publication Date
2024-04
Journal
The Journal of Organic Chemistry, v.89, no.7, pp.4647 - 4656
Publisher
American Chemical Society
Abstract
Herein, we describe the synthesis of substituted oxepane derivatives through the skeletal remodeling of 4-hydroxy-2-cyclobutenones, which are readily prepared from commercially available dialkyl squarates upon their reaction with acrylonitrile. Mechanistically, a Rh(I)-catalyzed C-C bond formation and cleavage cascade is proposed. Specifically, a fused [3.2.0] bicycle is proposed to form from dialkyl squarate-derived cyclobutenols via an unusual Rh(I)-catalyzed intermolecular oxa-Michael addition of a tertiary alcohol with acrylonitrile, followed by an intramolecular conjugate addition/migratory insertion. Subsequent C(sp3)-C(sp3) bond cleavage through a Rh-catalyzed β-carbon elimination is then theorized to furnish the oxepane scaffold. Computational studies support the formation of an intermediate [3.2.0] bicycle but also point to an alternative pathway for the formation of the oxepane products involving a Rh(III) intermediate. Additional studies have shown the overall process to be stereoretentive. The functional groups that are introduced in this process can be leveraged to form fused or bridged ring systems. © 2024 American Chemical Society.
URI
https://pr.ibs.re.kr/handle/8788114/15098
DOI
10.1021/acs.joc.3c02914
ISSN
0022-3263
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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