Abstract
Asymmetrized tris (hydroxymethyl)methane (THYM*)and bis (hydroxymethyl)acetaldehyde (BHYMA*) are new polyfunctionalized chiral building blocks prepared in high optical purity (e.e. 97%) by a chemoenzymatic procedure which utilizes as key step PPL catalyzed monohydrolysis of 2-(E)-alkenyl-1,3-diacetoxypropanes. A careful study on the effect of unsaturations adjacent to the prochiral center in a series of 2-substituted-l,3-diacetoxypropanes has unveiled an unprecedented dramatic effect of the double bond geometry on the absolute configuration of the resulting monoacetate. A tentative empirical model for the active site of PPL, able to rationalize these and other results, and based both on polarity and steric factors, is proposed. Several synthetic applications, which demonstrate the high chemical and stereochemical versatility of THYM* and BHYMA* are described.
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© 1992 Springer Science+Business Media Dordrecht
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Guanti, G., Banfi, L., Narisano, E. (1992). Asymmetrized Tris (Hydroxymethyl)Methane and Related Synthons as New Highly Versatile Chiral Building Blocks. Chemoenzymatic Preparation and Synthetic Applications. In: Servi, S. (eds) Microbial Reagents in Organic Synthesis. NATO ASI Series, vol 381. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-2444-7_24
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DOI: https://doi.org/10.1007/978-94-011-2444-7_24
Publisher Name: Springer, Dordrecht
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