Access to syn α‐Amino‐β‐Hydroxyesters by N‐H Insertion on O‐Protected α‐Diazo‐β‐Hydroxyesters. DOI Creative Commons

Thomas Defuentes,

Jérôme Lhoste, Catherine Gaulon‐Nourry

et al.

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

Published: Nov. 13, 2024

Abstract The N−H insertion reaction is a versatile method for creating C−N bonds under mild conditions, providing in particular an efficient access to both natural and non‐natural α‐amino acid derivatives. In this field, the direct on α‐diazo‐β‐hydroxyesters has not yet been investigated constitutes significant challenge, due competitive migration processes. We report herein first insertions O ‐protected α‐diazo‐β‐aryl‐β‐hydroxyesters, enabling synthesize wide range of α‐amino‐β‐hydroxyesters by tuning nature amine aryl substituent. Overall, 28 products have isolated, with moderate good yields most cases, diastereoisomeric ratios up 8.0 : 1 favor syn diastereoisomer.

Language: Английский

A visible-light-promoted metal-free approach for N–H insertions by using donor/donor diazo precursors DOI Creative Commons
Yu Zhang, Qiannan Li, Ping Wang

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(8), P. 4600 - 4608

Published: Jan. 1, 2024

A metal-free and catalyst-free strategy is reported to achieve N–H insertions by coupling N -tosylhydrazones with diverse amines including aminopyridines, anilines, aliphatic amines, other nucleophiles such as imidazoles indoles.

Language: Английский

Citations

11
Enantioselective organocatalytic strategies to access noncanonical α-amino acids DOI Creative Commons
Pietro Pecchini, Mariafrancesca Fochi, Francesca Bartoccini

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 5832 - 5868

Published: Jan. 1, 2024

Organocatalytic asymmetric synthesis has evolved over the years and continues to attract interest of many researchers worldwide. Enantiopure noncanonical amino acids (ncAAs) are valuable building blocks in organic synthesis, medicinal chemistry, chemical biology. They employed elaboration peptides proteins with enhanced activities and/or improved properties compared their natural counterparts, as chiral catalysts, ligand design, for syntheses complex molecules, including products. The linkage ncAA enantioselective organocatalysis, subject this perspective, tries imitate biosynthetic process. Herein, we present contemporary earlier developments field organocatalytic activation simple feedstock materials, providing potential ncAAs diverse side chains, unique three-dimensional structures, a high degree functionality. These strategies, useful forging wide range C-C, C-H, C-N bonds combinations thereof, vary from classical name reactions, such Ugi, Strecker, Mannich most advanced concepts deracemisation, transamination, carbene N-H insertion. Concurrently, some interesting mechanistic studies/models, information on chirality transfer Finally, perspective highlights, through diversity (AAs) not selected by nature protein incorporation, generic modes activation, induction, reactivity commonly used, enamine, hydrogen bonding, Brønsted acids/bases, phase-transfer reflecting increasingly important role applied chemistry.

Language: Английский

Citations

8
Enantioselective synthesis of chiral amides by carbene insertion into amide N–H bond DOI Creative Commons

Xuan-Ge Zhang,

Zhi‐Chun Yang,

Jia‐Bin Pan

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 5, 2024

Chiral amides are important structure in many natural products and pharmaceuticals, yet their efficient synthesis from simple amide feedstock remains challenge due to its weak Lewis basicity. Herein, we describe our study of the enantioselective chiral by N-alkylation primary taking advantage an achiral rhodium squaramide co-catalyzed carbene N-H insertion reaction. This method features mild condition, rapid reaction rate (in all cases 1 min) a wide substrate scope with high yield excellent enantioselectivity. Further product transformations show synthetic potential this Mechanistic studies reveal that non-covalent interactions between catalyst intermediate play critical role enantiocontrol.

Language: Английский

Citations

7
Overview of Transition Metal Catalyzed Multicomponent Reactions Based on Trapping of Allylic Electrophiles DOI

Kriti Gupta,

Mahesh Singh Harariya,

Arushi Tyagi

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(4)

Published: Jan. 11, 2024

Abstract Multicomponent reactions provide an excellent approach toward quaternary carbon centres utilizing convergent chemical in a highly selective manner under one‐pot conditions. The reactivity of substrates and metal catalysts is carefully controlled, precluding the formation side‐products. In this context, transition catalyzed onium ylides generated via diazo precursors nucleophiles with third component (an electrophile) have garnered significant attention. Using allylic precursor as electrophilic partner provides opportunities to construct all‐carbon centres. Furthermore, presence allyl fragment multicomponent product serves pivotal handle for carrying out subsequent modifications. Several recent studies employed Rh, Pd, dual Rh/Pd catalytic systems involving alkylation that proceed synergistic or relay pathway. Although not significantly successful, few cases, asymmetric induction achieved through chiral phosphoric acids phosphine ligands. Limited substrate catalyst scope underlying mechanistic complexities posed formidable challenges, slowing advancement reactions. This review details using readily available like compounds, carbonates, (R‐OH, R‐NH 2 , etc .) forming complex organic compounds. Our primary objective discuss issues may facilitate progress field.

Language: Английский

Citations

6
Rh‐Catalyzed Chemodivergent [3+3] Annulations of Diazoenals and α‐Aminoketones: Direct Synthesis of Functionalized 1,2‐Dihydropyridines and Fused 1,4‐Oxazines DOI
Pratap Kumar Mandal, Sreenivas Katukojvala

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(19)

Published: Jan. 2, 2024

Novel rhodium-catalyzed [3+3] annulations of diazoenals and α-amino ketones has been disclosed here. The reactivity switched from carbenoid to vinylogous NH-insertion by altering acyclic cyclic ketones. In this direction, we report an efficient strategy synthesize 1,2-dihydropyridines (DHPs) fused 1,4-oxazines. Mechanistic investigation revealed that the formyl group is necessary for annulation cyclohexyl dictating factor NH- insertion. synthetic utility was demonstrated synthesizing piperidine, pyrido[1,2-a]indole, 2-pyridone scaffolds. Further, structural diversification 1,4-oxazines resulted in short synthesis hexahydroquinolin-2(1H)-ones, hexahydro quinolines tetrahydroquinolinones via ring opening rearrangement a new oxidative deformylation, respectively.

Language: Английский

Citations

5
General Ir-Catalyzed N–H Insertions of Diazomalonates into Aliphatic and Aromatic Amines DOI Creative Commons
Zhong Zhuang, Céline Besnard, Jérôme Lacour

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(5), P. 983 - 987

Published: Jan. 26, 2024

A general N–H insertion reactivity of acceptor–acceptor diazo malonate reagents is reported using [Ir(cod)Cl]2 as catalyst. large range amines, primary and secondary, aliphatic aromatic, possible. Mild temperatures, perfect substrate/reactant stoichiometry, good functional group compatibility render the process particularly attractive for (late-stage) functionalization amines.

Language: Английский

Citations

5
Rhodium(II)-Catalyzed N–H Insertions of Carbenes under Mechanochemical Conditions DOI
Sourav Biswas, Carsten Bolm

Organic Letters, Journal Year: 2024, Volume and Issue: 26(7), P. 1511 - 1516

Published: Feb. 15, 2024

Under mechanochemical conditions in a mixer mill, Rh

Language: Английский

Citations

4
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
Access to syn α‐Amino‐β‐Hydroxyesters by N‐H Insertion on O‐Protected α‐Diazo‐β‐Hydroxyesters. DOI Creative Commons

Thomas Defuentes,

Jérôme Lhoste, Catherine Gaulon‐Nourry

et al.

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

Published: Nov. 13, 2024

Abstract The N−H insertion reaction is a versatile method for creating C−N bonds under mild conditions, providing in particular an efficient access to both natural and non‐natural α‐amino acid derivatives. In this field, the direct on α‐diazo‐β‐hydroxyesters has not yet been investigated constitutes significant challenge, due competitive migration processes. We report herein first insertions O ‐protected α‐diazo‐β‐aryl‐β‐hydroxyesters, enabling synthesize wide range of α‐amino‐β‐hydroxyesters by tuning nature amine aryl substituent. Overall, 28 products have isolated, with moderate good yields most cases, diastereoisomeric ratios up 8.0 : 1 favor syn diastereoisomer.

Language: Английский

Citations

0