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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Stereoselective Synthesis of Highly Functionalized Bicyclo[2.1.0]pentanes by Sequential [2 + 1] and [2 + 2]
Brockton Keen1, Christina Cong2, Alberto Castanedo2
1Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, United States.
Abstract:
This study describes a method for the stereoselective synthesis of highly functionalized bicyclo[2.1.0]pentanes (housanes). The approach utilizes a two-step sequence, a silver- or gold-catalyzed cyclopropenation of alkynes followed by an intermolecular [2 + 2] photocycloaddition reaction with electron-deficient alkenes. The cyclopropenation is an established reaction of aryldiazoacetates. A regioselective [2 + 2] cycloaddition of the cyclopropane was developed using blue LED irradiation, a commercially available photocatalyst as a triplet-sensitizer, and low reaction temperature (-40 °C). The [2 + 2] cycloaddition is highly diastereoselective, and when enantioenriched cyclopropenes are used, it proceeds with enantioretention.
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