Total synthesis of indolizidine alkaloid (-)-209D: overriding substrate bias in the asymmetric rhodium-catalyzed [2+2+2] cycloaddition
- PMID: 19229912
- PMCID: PMC2747357
- DOI: 10.1002/anie.200805455
Total synthesis of indolizidine alkaloid (-)-209D: overriding substrate bias in the asymmetric rhodium-catalyzed [2+2+2] cycloaddition
Abstract
CO! You had me at hello: The use of chiral biphenyl-based phosphoramidite ligands on rhodium provides an efficient [2+2+2] cycloaddition between terminal alkyl alkynes and alkenyl isocyanates (see scheme). The cycloaddition proceeds through a CO migration pathway, and facilitates a rapid four-step asymmetric synthesis of indolizidine (-)-209D.
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References
-
- Crabb TA, Newton RF, Jackson D. Chem Rev. 1971;71:109–126.
-
-
For a recent review on cylindricines, see: Weinreb SM. Chem Rev. 2006;106:2531–2549.
-
-
-
For total syntheses, see: Snider BB, Lin H. J Am Chem Soc. 1999;121:7778–7786.Scheffler G, Seike H, Sorensen EJ. Angew Chem Int Ed. 2000;39:4593–4596.Ousmer M, Braun NA, Bavoux C, Perrin M, Ciufolini MA. J Am Chem Soc. 2001;123:7534–7538.Maeng J, Funk RL. Org Lett. 2001;3:1125–1128.Kan T, Fujimoto T, Ieda S, Asoh Y, Kitaoka H, Fukuyama T. Org Lett. 2004;6:2729–2731.
-
-
- Liu P, Hong S, Weinreb SM. J Am Chem Soc. 2008;130:7562–7563. - PubMed
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