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Synfacts 2006(2): 0130-0130  
DOI: 10.1055/s-2005-924815
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Asymmetric Hydroformylation of [2.2.1]-Bicyclic Olefins

Contributor(s): Hisashi Yamamoto, Matthew B. Boxer
J. Huang*, E. Bunel*, A. Allgeier, J. Tedrow, T. Storz, J. Preston, T. Correll, D. Manley, T. Soukup, R. Jensen, R. Syed, G. Moniz, R. Larsen, M. Martinelli, P. J. Reider
Amgen Inc., Thousand Oaks, USA
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Publikationsdatum:
23. Januar 2006 (online)

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Significance

Hydroformylation of olefins is an industrial and medicinally important transformation. The use of Rh(CO)2(acac)/TangPhos was found to be suitable for the asymmetric hydroformylation of [2.2.1]-bicyclic olefins. Numerous chiral bidentate P,P ligands were screened and TangPhos gave the highest enantioselectivities (>90% ee in some cases). The enantioselectivities seemed to be relatively independent of temperature and CO/H2 pressure (see scheme). While the majority of substrates were based on the [2.2.1]-bicyclic framework, styrene was shown to be hydroformylated with a high branch/linear ratio (94:6) and in 76% ee, albeit with only 44% conversion.