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DOI: 10.1055/s-0033-1341062
Regioselectivity of Intramolecular Rhodium-Catalyzed C–H Insertion Reactions of α-Aryl-α-diazocarboxylates: Influence of the Aryl Substituent
Publication History
Received: 09 January 2014
Accepted after revision: 04 March 2014
Publication Date:
03 April 2014 (online)
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Abstract
It was found that α-aryl-α-diazocarboxylates react with variable regioselectivity in intramolecular rhodium-catalyzed C–H insertion reactions. 3-(Trialkoxysilyl)propyl esters underwent a clean cis-γ-lactone formation (62–69%) if the aryl rest was a phenyl group while the analogous α-(2-bromophenyl)-α-diazocarboxylates produced the respective β-lactones. In general β-lactone formation was shown to be the only detectable C–H insertion pathway for the latter substrate class irrespective of the ester substituent. The β-lactone products (eight examples) were obtained in yields of 41–68% with a diastereomeric ratio (dr) of 75:25 to 96:4 in favor of the trans diastereoisomer. The 2-bromo substituent could be displaced by an aryl group in a subsequent Suzuki cross-coupling reaction.
Key words
carbene complexes - diastereoselectivity - insertion - lactones - regioselectivity - rhodium - ring closureSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett. Included are procedures and analytical data for all new compounds.
- Supporting Information
Primary Data
- for this article are available online at http://www.thieme-connect.com/ejournals/toc/synthesis and can be cited using the following DOI: 10.4125/pd0057th. FIDs and associated files for the 1H and 13C NMR spectra for compounds 5, 6, 7, 8, 11, and 15 are provided.
- Primary Data
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