A short asymmetric synthesis of methyl 2-((1S,3R)-3-((tert-butyldiphenylsilyl)oxy)cyclopentyl)acetate from norbornene

[Display omitted] •Pd-(S)-MOP catalyzed hydrosilation of norbornene gives modest dr (84:16, exo/endo)•(S)-MOP catalyzed hydrosilation of norbornene gives 99%ee of exo and endo products.•(1R,4S)-stereochemistry is formed at the bridgehead carbons after oxidation.•Tandem oxidation/Baeyer-Villiger of norborneol leads to chiral bicyclic lactones.•The current route is competitive with established π-allyl desymmetrization methods. Methyl 2-((1S,3R)-3-((tert-butyldiphenylsilyl)oxy)cyclopentyl)acetate has been synthesized from norbornene using Hayashi’s (S)-MOP Pd-catalyzed asymmetric hydrosilation. On a 1 mol scale, asymmetric hydrosilation of norbornene afforded an 84:16 exo- to endo-norborneol mixture but with exclusive 1R,4S-stereochemistry at the bridgehead carbons. The norborneol mixture was converted to an optically pure chiral bicyclic lactone via a high-yielding tandem oxidation/Baeyer-Villiger reaction. Acid-promoted ring-opening of the lactone followed by immediate silyl protection afforded the chiral cis-1,3-cyclopentane intermediate in five steps with an overall yield of 41%.