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

doi:10.1016/S1872-2067(26)65117-0

Abstract

Abstract:

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.

Key words: Asymmetric catalysis, Azidoalcohols, Biomimetic chemistry, Hydrogen peroxide, Syn-addition, Manganese, Mechanism

Vladimir I. Kurganskii, Dmitry P. Lubov, Alexander G. Medvedev, Ruihu Wang, Konstantin P. Bryliakov. Bioinspired asymmetric syn-hydroxyazidation of electron-deficient olefins in the presence of nonheme Mn complexes[J]. Chinese Journal of Catalysis, 2026, 88: 468-477.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65117-0

https://www.cjcatal.com/EN/Y2026/V88/I9/468

Figures/Tables 5

Fig. 1. Time profiles of chalcone oxidation with H2O2 (2.3 equiv.) in HFIP:CH2Cl2 (2:1 v/v) in the presence of (S,S)-10 (1 mol%) and TMSN3 (2 equiv.) at ?20 °C. Relative concentrations: substrate (11a) black, epoxide (12a) blue, hydroxy azide (13a) olive. Enantiomeric excess: epoxide (ee of 12a) red, hydroxy azide (ee of 13a) orange.

Fig. 2. X-ray molecular crystal structure of the hydroxyl azide 13b. Ellipsoids are drawn at the 50% probability level. C gray, O red, H light gray.

Scheme 1. Proposed mechanisms of 2,3-hydroxy acyloxylation (top, cf. Ref. [28]) and 2,3-hydroxy azidation (bottom).

Fig. 3. Hammett plots of Log{(100+ee)/(100−ee)} vs. σ+p for the hydroxyazidation of p-substituted chalcones by the systems 8/TMSN3/H2O2 (A) and 10/ TMSN3/H2O2 (B).

Scheme 2. Examples of semi-preparative syntheses of chiral syn (A) and anti (B) 2-hydroxy-3-azides using bioinspired Mn complexes as catalysts.

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