Asymmetric approach to the pentacyclic skeleton of Aspidosperma alkaloids via enantioselective intramolecular 1,3-dipolar cycloaddition of carbonyl ylides catalyzed by chiral dirhodium(II) carboxylates

• Nambu, Hisanori

• Hikime, Mayuka

• Krishnamurthi, Janagiraman

• Kamiya, Megumi

• Shimada, Naoyuki

• Hashimoto, Shunichi

Abstract

This paper describes asymmetric tandem carbonyl ylide formation-intramolecular 1,3-dipolar cycloaddition reaction of diazo imides containing a tethered indole catalyzed by chiral dirhodium(II) carboxylates as an approach to the pentacyclic skeleton of Aspidosperma alkaloids. The cycloaddition of carbonyl ylides derived from indolyl-substituted 2-diazo-5-imido-3-ketoesters under the influence of dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], Rh2(S-TCPTTL)4, provides cycloadducts in moderate yields and enantioselectivities of up to 66% ee as well as with perfect endo diastereoselectivity. This is the first example of asymmetric induction in an intramolecular cycloaddition of a carbonyl ylide across an indolyl π-bond.

Journal

• Tetrahedron Letters

  Tetrahedron Letters 50 (26), 3675-3678, 2009-07-01

  Elsevier Ltd.

Keywords

• Carbonyl ylides
• 1,3-Dipolar cycloadditions
• Chiral dirhodium(II) carboxylates
• Vindorosine

Details

• CRID: 1050001339000980096
• NII Article ID: 120001390979
• HANDLE: 2115/38752
• ISSN: 00404039
• Text Lang: en
• Article Type: journal article
• Data Source:
  • IRDB
  • CiNii Articles