Precise Control of Regioselective N¹ and N²-Alkylation of Benzotriazoles with α-Diazoacetates by Metalloporphyrin

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Regioselective

Language: Английский

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Highly diastereoselective and enantioselective cyclopropanation of alkenes catalyzed by a chiral iridium(III) porphyrin complex

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101262 - 101262

Published: Feb. 1, 2025

Language: Английский

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Designing Ruthenium Phthalocyanine with Chiral Pockets Formed by (1R,2S,5R)-Menthoxy Groups for Enantioselective Catalysis

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4984 - 5001

Published: March 10, 2025

Unprecedented chiral ruthenium(II) complexes with phthalocyanines having motifs near the catalytic metal site have been prepared by cross condensation of 3,6-bis-aryloxy-phthalonitrile (α-Ar*O)2Pn bearing two (1R,2S,5R)-menthoxy groups orthogonal to aromatic plane and (15-crown-5)phthalonitrile. Four containing menthyl (M) 15-crown-5 units (C), notably RuPc[MC3](CO), RuPc[opp-M2C2](CO), RuPc[adj-M2C2](CO), RuPc[M3C](CO), were isolated in pure form fully characterized UV–vis, circular dichroism, HRMS, various 1H NMR 13C techniques. Their evaluation benchmark asymmetric cyclopropanation reaction styrene derivatives ethyl diazoacetate indicated that RuPc[opp-M2C2](CO) complex was most efficient terms diastereo- enantioselectivity. Further study revealed strong dependence stereoselectivity on solvent nature salt additives, which caused conformational rearrangement flexible surrounding, as evidenced multinuclear CD spectra. For instance, upon moving from commonly used CH2Cl2 EtOH addition NaPF6, a significant enhancement enantioselectivity (from 35 84% p-methylstyrene) obtained. Of particular importance is very high diastereoselectivity many substrates promoted incorporation sodium cations into crown ether cavities phthalocyanine attain trans/cis ratio up 499:1. Such regulating effect catalysis involving tetrapyrrolic has not previously observed, rendering this prominent example tunable catalyst. The developed synthetic strategy paves way environment around receptors tune properties.

Language: Английский

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Enantioselective Alkylation of Primary C(sp³)–H Bonds in N-Methyl Tertiary Amine Enabled by Iridium Complex of Axially Chiral β-Aryl Porphyrins

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

A fine-tuning of enantioselective carbene insertion into primary C(

Language: Английский

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