148585-93-7Relevant articles and documents
Catalytic enantioselective allyl- and crotylboration of aldehydes using chiral diol·SnCl4 complexes. Optimization, substrate scope and mechanistic investigations
Rauniyar, Vivek,Zhai, Huimin,Hall, Dennis G.
supporting information; scheme or table, p. 8481 - 8490 (2009/02/02)
We report a novel class of C2-symmetric chiral diols derived from the hydrobenzoin skeleton. The combination of these diols with SnCl 4 under Yamamoto's concept of Lewis acid assisted Bronsted acidity (LBA catalysis) leads to high levels of asymmetric induction in the allylboration of aldehydes by commercially available allylboronic acid pinacol ester 1a. The corresponding homoallylic alcohol products of synthetically useful aliphatic aldehydes are obtained in excellent yields with up to 98:2 er. This combined acid manifold is also efficient in catalyzing the diastereo- and enantioselective crotylboration of aldehydes, thus providing the propionate units in >95:5 dr and up to 98:2 er. The X-ray crystal structure of the optimal diol·SnCl4 complex, Vivol (4m)·SnCl 4, unambiguously shows the Bronsted acidic character of this LBA catalyst and its highly dissymmetrical environment. Further controls have ruled out a possible boron transesterification mechanism with the chiral diol and point to LBA catalyst-derived activation of the pinacol allylic boronates 1. Due to slow dissociation of the diol·SnCl4 complex, a small excess of diol is required in order to suppress a competing racemic cycle catalyzed by free SnCl4.
Scandium-catalyzed allylboration of aldehydes as a practical method for highly diastereo- and enantioselective construction of homoallylic alcohols
Lachance, Hugo,Lu, Xiaosong,Gravel, Michel,Hall, Dennis G.
, p. 10160 - 10161 (2007/10/03)
A general approach for the allylation of aldehydes using stable, air-tolerant camphor-based chiral allylboronates under Sc(OTf)3 catalysis is described. This practical methodology provides both syn and anti propionate units and other homoallylic alcohols with very high levels of diastereo- and enantioselectivity for several substrates, including functionalized aliphatic aldehydes useful toward the elaboration of complex natural products. Copyright