Details

Autor(en) / Beteiligte

• Liu, Cheng‐Hang
• Yu, Zhi‐Xiang

Titel

Rhodium(I)‐Catalyzed Bridged [5+2] Cycloaddition of cis‐Allene‐vinylcyclopropanes to Synthesize the Bicyclo[4.3.1]decane Skeleton

Ist Teil von

• Angewandte Chemie International Edition, 2017-07, Vol.56 (30), p.8667-8671

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2017

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Previously reported was that cis‐ene‐vinylcyclopropanes (cis‐ene‐VCPs) underwent Rh‐catalyzed [5+2] reaction to give 5,7‐fused bicyclic products, where vinylcyclopropane (VCP) acts as five‐carbon synthon. Unfortunately, this reaction had very limited scope. Replacing the 2π component of cis‐ene‐VCPs to allene moiety, the corresponding cis‐allene‐VCPs did not undergo the expected normal [5+2] cycloaddition to give 5,7‐fused bicyclic products. Instead, the challenging bicyclo[4.3.1]decane skeleton was obtained via an unprecedented bridged [5+2] cycloaddition. DFT calculations were applied to understand why this bridged [5+2] reaction is favored over the anticipated but not realized normal [5+2] reaction. Building bridges: Rhodium‐catalyzed reaction of cis‐allene‐vinylcyclopropanes did not give the anticipated fused bicyclic products through normal [5+2] reaction. Instead, these substrates underwent an unexpected bridged [5+2] cycloaddition, by inverse allene insertion, compared to normal allene insertion, thus generating the bicyclo[4.3.1]decane skeleton.