A Combination of Computational and Experimental Studies to Correlate Electronic Structure and Reactivity of Donor–Acceptor Singlet Carbenes DOI
Subhabrata Sen, Debajit Maiti,

Shweta Singh

et al.

Synlett, Journal Year: 2023, Volume and Issue: 35(03), P. 319 - 324

Published: Aug. 14, 2023

Abstract Most of the reactivities donor–acceptor (D–A) singlet carbenes are similar to metal carbenoids. However, lone pair at carbenoid carbon, coordinated with metal, is free in D–A carbene thereby making it nucleophilic as well. Herein, DFT-optimized structural features has been investigated and compared rhodium carbenoid. It was observed that, when a reacts cyclic-1,3-diones different ethereal solvents, sp2 orbital that abstracts proton from enol form (of cyclic-1,3-diones) benzylic carbocation an enolate. Subsequently, undergoes attack by O ether solvents then enolate afford desired ether-linked products. Accordingly, herein reaction THF, which otherwise had failed work substrate reported amino etherification reactions, worked DFT-calculated energy levels profile support this reverse reactivity carbenes. Furthermore, HOMO–LUMO calculations indicated electron-rich arenes stabilizes LUMO destabilizes HOMO increases yield. Additionally, library 37 39 compounds potential medicinal relevance have synthesized good excellent yields using numerous cyclic-1,3-diones.

Language: Английский

Catalytic N‐H Insertion Reactions with α‐Diazoacetates: An Efficient Method for Enantioselective Amino Acid Synthesis DOI

Yu‐Xuan Su,

Ming‐Yao Huang, Shou‐Fei Zhu

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(15)

Published: May 30, 2023

Abstract As the monomers of proteins, amino acids are critical in chemistry and biology, playing important roles multiple fields such as synthetic chemistry, medicinal materials chemistry. Unlike proteinogenic acids, unnatural can be difficult to obtain from living organisms generally synthesized chemically. Recently, a method involving asymmetric N−H bond carbene insertion reaction with α‐diazoacetates precursor has shown high enantioselectivity good functional group tolerance, allowing for facile synthesis natural introduction new concepts catalysis.

Language: Английский

Citations

9
Enantioselective N–H Bond Insertion Reaction of Anilines Enabled by Ruthenium and Chiral Phosphoric Acid Cooperative Catalysis DOI

Shaoran An,

Yan Zhu, Jiangtao Sun

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6214 - 6219

Published: July 17, 2024

The enantioselective carbene insertion into N-H bonds of anilines has been realized by cooperative catalysis ruthenium complexes and chiral phosphoric acids, providing the expected α-aryl glycines in moderate to good yields with high enantioselectivity. Typically, slightly modifying reaction conditions, this approach allows bond be effective for both α-alkyl diazoacetates first time enantioselectivity (up 96% 95% ee, respectively).

Language: Английский

Citations

3
Chiral N,N′-dioxide/Mg(OTf)2 complex-catalyzed asymmetric [2,3]-rearrangement of in situ generated ammonium salts DOI Creative Commons
Qianchi Lin, Bowen Hu, Xi Xu

et al.

Chemical Science, Journal Year: 2020, Volume and Issue: 11(11), P. 3068 - 3073

Published: Jan. 1, 2020

The Lewis acid catalyzed asymmetric [2,3]-rearrangement of quaternary ammonium ylides formed in situ from glycine pyrazoleamides and allyl bromides.

Language: Английский

Citations

21
Asymmetric synthesis of dihydro-1,3-dioxepines by Rh(ii)/Sm(iii) relay catalytic three-component tandem [4 + 3]-cycloaddition DOI Creative Commons
Chaoran Xu,

Jianglin Qiao,

Shunxi Dong

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(15), P. 5458 - 5463

Published: Jan. 1, 2021

Catalytic asymmetric tandem carbonyl ylide formation/[4 + 3]-cycloaddition of β,γ-unsaturated α-ketoesters, aldehydes and α-diazoacetates was achieved by using a bimetallic rhodium(ii)/chiral N,N′-dioxide–Sm(iii) complex catalyst.

Language: Английский

Citations

19
Asymmetric Sonogashira C(sp3)–C(sp) bond coupling enabled by a copper(i) complex of a new guanidine-hybrid ligand DOI

Jinzhao Li,

Lichao Ning, Qingfa Tan

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(22), P. 6312 - 6318

Published: Jan. 1, 2022

A type of new chiral nitrogen-donor hybrid ligand bearing acyclic guanidine, amide, and pyridine subunits was rationalized for Cu( i )-catalyzed asymmetric Sonogashira C(sp 3 )–C(sp) cross-coupling.

Language: Английский

Citations

14
α‐Amination of Carbonyl Compounds by Using Hypervalent Iodine‐Based Aminating Reagents Containing a Transferable (Diarylmethylene)amino Group DOI

Daichi Okumatsu,

Kazuki Kawanaka,

Shunpei Kainuma

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(10)

Published: Jan. 6, 2023

Hypervalent iodine-based aminating reagents containing a transferable (diarylmethylene)amino group can be used for the α-amination of simple carbonyl compounds such as esters, amides, and ketones in presence lithium base. The groups products readily modified, thus providing access to primary amines diarylmethylamines. developed method features transition-metal-free conditions one-pot procedure without need prepare enolate equivalents separately, offering general practical approach synthesis wide variety α-amino compounds. Experimental mechanistic investigations indicate that this amination proceeds through unique radical coupling an α-carbonyl with iminyl radical; they are generated single-electron transfer between hypervalent iodine reagent.

Language: Английский

Citations

8
An asymmetric hydrocyanation/Michael reaction of α-diazoacetates via Cu(i)/chiral guanidine catalysis DOI
Sai Ruan, Xia Zhong, Quangang Chen

et al.

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(14), P. 2155 - 2158

Published: Jan. 1, 2020

An asymmetric one-pot hydrocyanation/Michael reaction of α-aryl diazoacetates with trimethylsilyl cyanide, tert-butanol, and N-phenylmaleimides has been realized. Using a chiral guanidinium salt/CuBr catalyst, series cyanide-containing pyrrolidine-2,5-diones could be obtained in good yields excellent diastereo- enantioselectivities.

Language: Английский

Citations

18
Copper-Catalyzed Defluorinative [3 + 2] Cyclization of Amidines and Trifluoromethyl Carbenoids for the Synthesis of 5-Fluoroimidazoles DOI
Jinxin Liu, Hao Tan, Yonghong Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(43), P. 9363 - 9367

Published: Oct. 18, 2024

A Cu-catalyzed [3 + 2] cyclization of amidines with trifluoromethyldiazo compounds is described. The reaction affords 5-fluoroimidazoles in good yields by cleaving dual C–F bonds a CF3 group. Using 2-aminoazo heterocycles as the substrates, various annelated imidazoles containing fluorine atom were also constructed this method without changing conditions. resultant show high reactivity toward SNAr reactions series nucleophiles.

Language: Английский

Citations

2
Recent Progress towards the Use of Benzophenone Imines as an Ammonia Equivalent DOI Open Access
Yuta Kondo, Hiroyuki Morimoto, Takashi Ohshima

et al.

Chemistry Letters, Journal Year: 2020, Volume and Issue: 49(5), P. 497 - 504

Published: Feb. 28, 2020

Benzophenone imine and its derivatives are useful ammonia equivalents for synthesizing primary amines, readily achieving the selective formation of amines obtaining easily deprotectable...

Language: Английский

Citations

13
Synthesis of functionalized 3,2′-pyrrolidinyl spirooxindoles via domino 1,6-addition/annulation reactions of para-quinone methides and 3-chlorooxindoles DOI
Xiaochen Tian, Yongxing Zhang, Weiwu Ren

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 9(3), P. 615 - 626

Published: Dec. 20, 2021

A highly efficient diastereoselective [4 + 1] cycloaddition of ortho -tosylaminophenyl-substituted p -QMs with 3-chlorooxindoles has been developed to afford 3,2′-pyrrolidinyl spirooxindoles.

Language: Английский

Citations

11