Ti-Salan catalyzed asymmetric sulfoxidation of pyridylmethylthiobenzimidazoles to optically pure proton pump inhibitors

Standard

Ti-Salan catalyzed asymmetric sulfoxidation of pyridylmethylthiobenzimidazoles to optically pure proton pump inhibitors. / Talsi, Evgenii P.; Bryliakov, Konstantin P.

In: Catalysis Today, Vol. 279, 01.01.2017, p. 84-89.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{f53d71d1936c43afbdd084054b89aa0a,

title = "Ti-Salan catalyzed asymmetric sulfoxidation of pyridylmethylthiobenzimidazoles to optically pure proton pump inhibitors",

abstract = "The asymmetric sulfoxidation of two pyridylmethylthiobenzimidazoles to anti-ulcer drugs of the PPI family (S)-omeprazole and (R)-lansoprazole with hydrogen peroxide, mediated by a series of chiral titanium(IV) salan complexes is reported. High sulfoxide yields (up to >95%) and enantioselectivities (up to 94% ee) have been achieved. The introduction of electron-withdrawing substituents leads to less active and less enantioselective catalysts. Like for the previously reported Ti-salalen catalyzed sulfoxidations, the temperature dependence of the sulfoxidation enantioselectivity in the presence of Ti-salan complexes is nonmonotonic, demonstrating isoinversion behavior with decreasing temperature. The oxidation is likely rate-limited by the formation of the active (presumably peroxotitanium(IV)) species, followed by a faster oxygen transfer to the substrate.",

keywords = "Asymmetric oxidation, Esomeprazole, Hydrogen peroxide, Isoinversion, Mechanism, Salan, Titanium, OXIDATION, SULFIDES, AQUEOUS HYDROGEN-PEROXIDE, RESOLUTION, COMPLEXES, ENANTIOSELECTIVE SULFOXIDATION, EPOXIDATION, CHIRAL SULFOXIDES, VANADIUM CATALYSTS, WATER",

author = "Talsi, {Evgenii P.} and Bryliakov, {Konstantin P.}",

year = "2017",

month = jan,

day = "1",

doi = "10.1016/j.cattod.2016.03.006",

language = "English",

volume = "279",

pages = "84--89",

journal = "Catalysis Today",

issn = "0920-5861",

publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Ti-Salan catalyzed asymmetric sulfoxidation of pyridylmethylthiobenzimidazoles to optically pure proton pump inhibitors

AU - Talsi, Evgenii P.

AU - Bryliakov, Konstantin P.

PY - 2017/1/1

Y1 - 2017/1/1

N2 - The asymmetric sulfoxidation of two pyridylmethylthiobenzimidazoles to anti-ulcer drugs of the PPI family (S)-omeprazole and (R)-lansoprazole with hydrogen peroxide, mediated by a series of chiral titanium(IV) salan complexes is reported. High sulfoxide yields (up to >95%) and enantioselectivities (up to 94% ee) have been achieved. The introduction of electron-withdrawing substituents leads to less active and less enantioselective catalysts. Like for the previously reported Ti-salalen catalyzed sulfoxidations, the temperature dependence of the sulfoxidation enantioselectivity in the presence of Ti-salan complexes is nonmonotonic, demonstrating isoinversion behavior with decreasing temperature. The oxidation is likely rate-limited by the formation of the active (presumably peroxotitanium(IV)) species, followed by a faster oxygen transfer to the substrate.

AB - The asymmetric sulfoxidation of two pyridylmethylthiobenzimidazoles to anti-ulcer drugs of the PPI family (S)-omeprazole and (R)-lansoprazole with hydrogen peroxide, mediated by a series of chiral titanium(IV) salan complexes is reported. High sulfoxide yields (up to >95%) and enantioselectivities (up to 94% ee) have been achieved. The introduction of electron-withdrawing substituents leads to less active and less enantioselective catalysts. Like for the previously reported Ti-salalen catalyzed sulfoxidations, the temperature dependence of the sulfoxidation enantioselectivity in the presence of Ti-salan complexes is nonmonotonic, demonstrating isoinversion behavior with decreasing temperature. The oxidation is likely rate-limited by the formation of the active (presumably peroxotitanium(IV)) species, followed by a faster oxygen transfer to the substrate.

KW - Asymmetric oxidation

KW - Esomeprazole

KW - Hydrogen peroxide

KW - Isoinversion

KW - Mechanism

KW - Salan

KW - Titanium

KW - OXIDATION

KW - SULFIDES

KW - AQUEOUS HYDROGEN-PEROXIDE

KW - RESOLUTION

KW - COMPLEXES

KW - ENANTIOSELECTIVE SULFOXIDATION

KW - EPOXIDATION

KW - CHIRAL SULFOXIDES

KW - VANADIUM CATALYSTS

KW - WATER

UR - http://www.scopus.com/inward/record.url?scp=85025669397&partnerID=8YFLogxK

U2 - 10.1016/j.cattod.2016.03.006

DO - 10.1016/j.cattod.2016.03.006

M3 - Article

AN - SCOPUS:85025669397

VL - 279

SP - 84

EP - 89

JO - Catalysis Today

JF - Catalysis Today

SN - 0920-5861

ER -

ID: 9048827