Gold-catalyzed [2+2+1] cycloaddition of 1,6-diyne carbonates and esters with aldehydes to 4-(cyclohexa-1,3-dienyl)-1,3-dioxolanes

• Main Authors: Rao, Weidong, Chan, Philip Wai Hong
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2014
• Subjects: DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis
• Online Access: https://hdl.handle.net/10356/100970; http://hdl.handle.net/10220/19019
• Institution: Nanyang Technological University

A synthetic method to stereoselectively prepare 4-(cyclohexa-1,3-dienyl)-1,3-dioxolanes in good to excellent yields by gold(I)-catalyzed [2+2+1] cycloaddition of 1,6-diyne carbonates and esters with aldehydes is described. The cascade process involves 1,2-acyloxy migration followed by cyclopropenation and cycloreversion. This leads to an unprecedented [2+2+1] cycloaddition of the resulting alkenylgold carbenoid species, examples of which are extremely rare, with two aldehyde molecules at catalyst loadings as low as 1 mol %. The usefulness of this cycloisomerization chemistry was further demonstrated by the transformation of one example to the corresponding phenol.