Lithium-stabilized nucleophilic addition of thiamin to a ketone provides an efficient route to mandelylthiamin, a critical pre-decarboxylation intermediate

Bioorganic Chemistry
Michael BieleckiRonald Kluger

Abstract

Mandelylthiamin (MTh) is an accurate model of the covalent intermediate derived from the condensation of thiamin diphosphate and benzoylformate in benzoylformate decarboxylase. The properties and catalytic susceptibilities of mandelylthiamin are the subjects of considerable interest. However, the existing synthesis gives only trace amounts of the precursor to MTh as it is conducted under reversible conditions. An improved approach derives from the unique ability of lithium ions to drive to completion the otherwise unfavorable condensation of the conjugate base of thiamin and methyl benzoylformate. The unique efficiency of the condensation reaction in the presence of lithium ions is established in contrast to the effects of other Lewis acids. Interpretation of the pattern of the results indicates that the condensation of the ketone and thiamin is thermodynamically controlled. It is proposed that the addition of lithium ions displaces the equilibrium toward the product through formation of a stable lithium-alkoxide.

References

Dec 12, 2002·Journal of the American Chemical Society·Qingyan Hu, Ronald Kluger
Sep 1, 2005·Journal of the American Chemical Society·Qingyan Hu, Ronald Kluger
Mar 21, 2007·Journal of the American Chemical Society·Asim K BeraMiriam S Hasson
May 22, 2008·Chemical Reviews·Ronald Kluger, Kai Tittmann
Nov 20, 2008·The FEBS Journal·Ronald Kluger, Steven Rathgeber
Aug 1, 2009·Journal of the American Chemical Society·Scott O C MundleRonald Kluger
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Dec 12, 2012·Journal of the American Chemical Society·Graeme W HoweRonald Kluger
Mar 20, 2014·Chemical Communications : Chem Comm·Dieter EndersAndreas Rembiak

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