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Study of the (1,7)-sigmatropic shift of a 1-hydroxylated 3-desoxy previtamin D to vitamin D: observation of a modest primary deuterium kinetic isotope effect/sup 1/

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00211a051· OSTI ID:5353213

Studies of 19,19,19-trideuteriated derivatives of previtamin D/sub 3/ and their various 1-hydroxylated counterparts invite the possibility of utilizing previtamins as biochemical or chemical research tools. It is anticipated that a heavy isotope at C-19 will attenuate the rate of the (1,7)-sigmatropic shift so as to facilitate handling of the thermally unstable previtamins. Thus, in the case of 1..cap alpha..,25-dihydroxyvitamin D/sub 3/, its previtamin form might be anticipated to exist in nature, and its more stable 19,19,19-trideuterio counterpart would facilitate evaluation of its biological profile. Moreover, the latter might have practical application as a slow release source of the highly potent, and potentially toxic, natural hormone. In this communication the authors describe their initial studies in this area through kinetic investigations of the isomerization of 3-deoxy-1-hydroxyprevitamin D/sub 3/ epimers, a (1,7)-sigmatropic shift model for the previtamin form of the natural hormone.

Research Organization:
Univ. of California, Riverside (USA)
OSTI ID:
5353213
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:3; ISSN JACSA
Country of Publication:
United States
Language:
English