D
A. Bhatia et al.
Letter
Synlett
anism for AAD of alcohols using compounds 1 and 2 in-
volved phosphine-dissociative pathway and ruthenium–hy-
dride complex as active catalyst. The mechanism of dehy-
drogenative lactonization of alcohols is closely related to
alcohol oxidation using 1, 2, and other reported catalysts.16
According to this mechanism, both compounds 1 and 2 un-
dergo triphenylphosphine dissociation followed by reaction
with alcohol and base to generate the Ru–hydride active
catalyst A. The active catalyst A undergoes oxidative addi-
tion with diol to form ruthenium alkoxide intermediate B,
followed by elimination of hydrogen molecule. β-Hydrogen
elimination of intermediate B resulted in hydroxyaldehyde
C, which further undergoes cyclization to form lactol D to
generate the active catalyst A. The active catalyst A under-
goes oxidative addition with lactol D, followed by elimina-
tion of hydrogen molecule to yield the Ru–H intermediate
E. Intermediate E further undergoes β-hydrogen elimina-
tion to form lactone F and the active catalyst A.
Supporting Information
Supporting information for this article is available online at
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References and Notes
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where n = 1 for 1
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Scheme 3 Mechanism for the lactonization of diols with catalyst 1 and 2
In conclusion, we have reported conversion of diols into
lactones in aqueous medium using ruthenium complexes 1
and 2 bearing PTA and pyridine-based chelating ligands. We
have also experimentally proved the formation of rutheni-
um hydride species as active catalyst and aldehyde inter-
mediate.
Funding Information
This work was supported by Science and Engineering Research Board,
India in the form of Start-Up Research Grant (Young Scientists, No.
58/FT /C5-092/2014). AB thanks DST, WOS-A of India for fellowship
(SR/WOS-A/CS-1035/2015).()
(8) Luca, G.; Antonella, G.; Frederic, H.; Donald, K. A.; Eric, M.;
Gianna, R.; Maurizio, P. Pure Appl. Chem. 2013, 85, 385; and ref-
erences cited therein.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–E