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Synthesis 2017; 49(02): 326-352
DOI: 10.1055/s-0036-1588338
paper
© Georg Thieme Verlag Stuttgart · New York

Two-Step Synthesis of (Z)-3-Aryl-5-(arylmethylidene)butenolides by an Ivanov Reaction/Silver(I)-Catalyzed Lactonization/In Situ Dehydration Sequence

David Hermann
,
Deniz Arican
,
Reinhard Brückner*
Further Information

Publication History

Received: 24 September 2016

Accepted: 26 September 2016

Publication Date:
14 November 2016 (online)

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Dedicated to Professor Dieter Enders (RWTH Aachen) on the occasion of his 70th birthday

Abstract

A stereoselective synthesis of the title compounds was developed. Hexane- and amine-free THF solutions of α-lithiated lithium arylacetates (‘arylacetic acid dianions’) were aldol-added to 3-arylpropynals. This gave 2,5-diaryl-3-hydroxypent-4-ynoic acids with up to a 72:28 preference for the anti-diastereomer (27 examples + 1 exception). When treated with Ag2CO3 (1–20 mol%) in DMF at room temperature for 2.5 days, the respective mixtures underwent regio- and stereoselective lactonizations followed by an in situ dehydration. Thereby 3-aryl-5-(arylmethylidene)butenolides were obtained with a Z-configuration of the oxygenated C=C bond. Their overall yields ranged from 46% to 83% (1 exception: 28%). Three 3-aryl-5-(arylmethyli­dene)butenolides contained a C–Br and/or a C–I bond. They allowed a subsequent Pd-catalyzed C–C coupling, which furnished follow-up butenolides.

Key words

aldol addition - cyclization - β-elimination - lactones - silver carbonate - stereoselectivity - tandem reaction

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588338.
  • Supporting Information
 

  • References

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