The growing importance of triarylarsines as ligands for transition metal catalysis has sparked recent interest in new synthetic routes to tertiary arsines that avoid hazardous arsenous chloride reagents. However, safer methods for the synthesis of lesser explored arsine heterocycles, especially those containing As-C(sp3) bonds, remain lacking. We demonstrate for the first time that bench stable...

The catalytic asymmetric synthesis of tertiary alcohols by the addition of organometallic reagents to ketones is of central importance in organic chemistry. The resulting quaternary stereocentres are difficult to prepare selectively by other means despite their widespread occurrence in natural products and pharmaceuticals. Here we report on a new methodology which allows access to both α-bromo-...

It has been found that nucleophilic reagents, i.e., NaBH4, Grignard reagents, and alkyl lithium, uniquely react with the -alkoxyor acyloxy-lactone moieties in ginkgolide and F-seco-ginkgolides to give rise to lactol derivatives. The reaction is rapid and stops at the lactol stage; the strong coordination of Na, Mg, and Li metals to the conformationally rigid cage structure is involved in both t...