Bioinspired asymmetric syn-hydroxyazidation of electron-deficient olefins in the presence of nonheme Mn complexes

Bioinspired asymmetric syn-hydroxyazidation of electron-deficient olefins in the presence of nonheme Mn complexes Full article

Journal

Chinese Journal of Catalysis
ISSN: 0253-9837 , E-ISSN: 1872-2067

Output data

Year: 2026, Volume: 88, Pages: 468-477 Pages count : 10 DOI: 10.1016/s1872-2067(26)65117-0

Authors

Kurganskii Vladimir I. ¹ , Lubov Dmitry P. ¹ , Medvedev Alexander G. ² , Wang Ruihu ³ , Bryliakov Konstantin P. ¹

Affiliations

1	Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr. 47, Moscow 119991, Russia
2	Kurnakov Institute of General and Inorganic Chemistry RAS, Leninsky Pr. 31, Moscow 119991, Russia
3	Hebei Key Laboratory of Functional Polymer, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China

Previously, chiral bis-amino-bis-pyridylmethyl and structurally related Mn complexes have been reported to mediate a variety of highly enantioselective biomimetic oxidative transformations of C=C groups with hydrogen peroxide, such as epoxidations, syn-1,2-dihydroxylations, and syn-1,2-hydroxy acyloxylations. Herein, we present one more facet of their versatile catalytic reactivity which enables the enantioselective conversion of olefinic substrates to the corresponding vicinal syn-hydroxy azides in up to 96% ee. The data collected here provide evidence in favor of the direct regio- and enantioselective vicinal syn-hydroxyazidation of the substrate, using H2O2 as terminal oxidant and TMSN3 as an azide source. Such reactivity is conceptually similar to that of Rieske dioxygenases, capable of adding two cis-substituents to the C=C group in a syn-selective fashion. The bioinspired catalyst systems discussed herein provide facile access to a variety of enantiomerically enriched 1,2,3-trifunctionalized compounds, featuring both syn and anti 2,3-hydroxy azide moieties.

Kurganskii V.I. , Lubov D.P. , Medvedev A.G. , Wang R. , Bryliakov K.P.
Bioinspired asymmetric syn-hydroxyazidation of electron-deficient olefins in the presence of nonheme Mn complexes
Chinese Journal of Catalysis. 2026. V.88. P.468-477. DOI: 10.1016/s1872-2067(26)65117-0 WOS Scopus OpenAlex

Submitted:	Feb 20, 2026
Accepted:	Mar 22, 2026
Published online:	Sep 5, 2026

≡ Web of science:	WOS:001845115600001
≡ Scopus:	2-s2.0-105046555209
≡ OpenAlex:	W7196954524