Asymmetric Carbene Insertion into Se‐S Bonds by Synergistic Rh(II)/Guanidine Catalysis Involving Chalcogen‐Bond Assistance DOI
Xin He,

Yihua Fu,

Ruiying Xi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 2, 2024

Abstract The efficient construction of chalcogen‐atom‐based chiral compounds remains a challenge, despite the importance organoselenium and organosulfur in life materials science. Chalcogen atoms can form net attractive interactions called chalcogen bonds, but it is an undeveloped tool to assist asymmetric catalysis. Herein, we report enantioselective insertion platform install stereogenic center bearing selenyl thiocyano functional groups. Our method operates by synergistic catalysis guanidine achiral dirhodium complex three‐component or four‐component reaction, through Se−S bond into carbene species, competing successfully with spontaneous racemic process showing high regioselectivity. As elucidated spectroscopic experiments computational studies, unique mechanism involving as well hydrogen bonding was established account for enantiocontrol. stereoselectivity holds broad array selenylthiocyanatopropanoates, which showed excellent anti‐inflammatory toward IL‐1β low cytotoxicity.

Language: Английский

B(C6F5)3·H2O-Catalyzed N–H and C–H Functionalization of Aromatic Amines with Sulfoxonium Ylides under Metal-Free Conditions DOI

Shenmeng Yan,

Yingdi Hao,

Shuran Xu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 31, 2024

Hydrogen-bonded aggregates of B(C6F5)3 and water are proven as strong Brønsted acid catalysts, which have the advantages low toxicity broad compatibility. Sulfoxonium ylides stable surrogates diazo compounds, participate in various reactions due to their versatile reactivity. Based on these characteristics, a strategy for C–N bond or C–C construction aromatic amines with sulfoxonium under metal-free catalytic conditions was established. This method has mild excellent yield, is suitable N–H C–H functionalization amine compounds.

Language: Английский

Citations

1
Systematic Studies of Functional Group Tolerance and Chemoselectivity in Carbene-Mediated Intramolecular Cyclopropanation and Intermolecular C–H Functionalization DOI Open Access

Haruki Kanda,

Ayaka Okabe,

Shingo Harada

et al.

Chemical and Pharmaceutical Bulletin, Journal Year: 2024, Volume and Issue: 72(3), P. 313 - 318

Published: March 15, 2024

Generating reliable data on functional group compatibility and chemoselectivity is essential for evaluating the practicality of chemical reactions predicting retrosynthetic routes. In this context, we performed systematic studies using a evaluation kit including 26 kinds additives to assess tolerance carbene-mediated reactions. Our findings revealed that some intermolecular heteroatom-hydrogen insertion proceed faster than intramolecular cyclopropanation Lewis basic functionalities inhibited rhodium-catalyzed C-H functionalization indoles. While performing these studies, observed an unexpected 1-naphthol variant used as additive.

Language: Английский

Citations

0
Iron(II) Phthalocyanine-Catalyzed Homodimerization and Tandem Diamination of Diazo Compounds with Primary Amines: Access to Construct Substituted 2,3-Diaminosuccinonitriles in One-Pot DOI
Gang Wang, Jiali Yuan, Rong Zhou

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7718 - 7726

Published: May 24, 2024

We herein first report the homodimerization and tandem diamination of diazo compounds with primary amines catalyzed by iron(II) phthalocyanine (PcFe(II)), which can construct one C-C bond two C-N bonds within 20 min in one-pot. Compared to traditional metal-catalyzed N-H insertion reaction between reagents, developed almost does not generate product, but homodimerization/tandem product. The proposed mechanism studies indicate that play a crucial role homocoupling via dimerization iron(III)-acetonitrile radical generated from diazoacetonitrile PcFe(II) coordinated bis(amines); β-hydride elimination is involved, then, attack toward carbon atoms on formed followed. Moreover, this novel be used effectively prepare substituted 2,3-diaminosuccinonitriles high yields even up >99:1 d.r., encouragingly these products contain both 1,2-diamines succinonitrile motifs, are classes important organic significant applications many yields. This also suitable for gram-scale preparation 2,3-bis(phenylamino)succinonitrile (

Language: Английский

Citations

0
Asymmetric Carbene Insertion into Se‐S Bonds by Synergistic Rh(II)/Guanidine Catalysis Involving Chalcogen‐Bond Assistance DOI
Xin He,

Yihua Fu,

Ruiying Xi

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 2, 2024

Abstract The efficient construction of chalcogen‐atom‐based chiral compounds remains a challenge, despite the importance organoselenium and organosulfur in life materials science. Chalcogen atoms can form net attractive interactions called chalcogen bonds, but it is an undeveloped tool to assist asymmetric catalysis. Herein, we report enantioselective insertion platform install stereogenic center bearing selenyl thiocyano functional groups. Our method operates by synergistic catalysis guanidine achiral dirhodium complex three‐component or four‐component reaction, through Se−S bond into carbene species, competing successfully with spontaneous racemic process showing high regioselectivity. As elucidated spectroscopic experiments computational studies, unique mechanism involving as well hydrogen bonding was established account for enantiocontrol. stereoselectivity holds broad array selenylthiocyanatopropanoates, which showed excellent anti‐inflammatory toward IL‐1β low cytotoxicity.

Language: Английский

Citations

0