Use of 2,3-bis(phenylsulfonyl)-1,3-butadiene as a reagent for the synthesis of azapolycyclic ring systems

作者：Flick Andrew C; Padwa Albert^*

来源：Journal of Sulfur Chemistry, 2013, 34(1-2): 7-16.

DOI：10.1080/17415993.2012.695793

• bis(phenylsulfonyl)diene
• Michael addition
• [2+2]-cycloaddition
• allene
• intramolecular
• carbanion rearrangement
• cyclization
• piperidine
• alkaloid

2,3-Bis(phenylsulfonyl)-1,3-butadiene undergoes ready Michael addition with various primary amines to ultimately produce dihydropyrrolidines by a mechanism involving a proton shift after the initial conjugate addition followed by a subsequent intramolecular cyclization. A related transformation occurs with soft carbanion nucleophiles such as malonate esters. N-Alkyl imines also react to produce tetrahydropyridines by a sequence of reactions involving the transient intermediacy of a 1,3-diphenylsulfonyl diene. When the malonate ester contains a tethered pi-bond, an initially formed allene undergoes a subsequent intramolecular [2+2]-cycloaddition to give bicyclo[4.2.0]-adducts.
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• 出版日期2013-4-1