Copper‐Catalyzed Enantioselective C(sp3)−SCF3 Coupling of Carbon‐Centered Benzyl Radicals with (Me4N)SCF3 DOI
Wei Zhang, Yu Tian, Xiaodong Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(11)

Published: Jan. 26, 2024

Abstract In contrast with the well‐established C(sp 2 )−SCF 3 cross‐coupling to forge Ar−SCF bond, corresponding enantioselective coupling of readily available alkyl electrophiles chiral bond has remained largely unexplored. We herein disclose a copper‐catalyzed radical range secondary/tertiary benzyl radicals easily (Me 4 N)SCF reagent. The key success lies in utilization phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for simultaneous control reaction initiation enantioselectivity. This strategy can successfully realize two types asymmetric reactions, including enantioconvergent racemic halides three‐component 1,2‐carbotrifluoromethylthiolation arylated alkenes under mild conditions. It therefore provides highly flexible platform rapid assembly an array enantioenriched SCF ‐containing molecules interest organic synthesis medicinal chemistry.

Language: Английский

Copper‐Catalyzed Enantioselective C(sp3)−SCF3 Coupling of Carbon‐Centered Benzyl Radicals with (Me4N)SCF3 DOI
Wei Zhang, Yu Tian, Xiaodong Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(11)

Published: Jan. 26, 2024

Abstract In contrast with the well‐established C(sp 2 )−SCF 3 cross‐coupling to forge Ar−SCF bond, corresponding enantioselective coupling of readily available alkyl electrophiles chiral bond has remained largely unexplored. We herein disclose a copper‐catalyzed radical range secondary/tertiary benzyl radicals easily (Me 4 N)SCF reagent. The key success lies in utilization phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for simultaneous control reaction initiation enantioselectivity. This strategy can successfully realize two types asymmetric reactions, including enantioconvergent racemic halides three‐component 1,2‐carbotrifluoromethylthiolation arylated alkenes under mild conditions. It therefore provides highly flexible platform rapid assembly an array enantioenriched SCF ‐containing molecules interest organic synthesis medicinal chemistry.

Language: Английский

Citations

10

Photoinduced Copper-Catalyzed Regio- and Enantioselective Alkynylation of Epoxides DOI

Jianye Li,

Sijia Li,

Guo-Hao Cui

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7553 - 7561

Published: May 1, 2024

Epoxides are privileged and valuable electrophiles frequently utilized as versatile building blocks in synthetic chemistry to prepare diverse alcohols through ring-opening reactions. However, the catalytic stereoconvergent cross-coupling of racemic epoxides with electro- or nucleophiles has remained a persistent challenge. In this work, we present mild method achieve regio- enantioselective alkynylation various alkynes, resulting synthesis β-chiral homopropargyl via photoinduced copper-based system. The use monofluoro-substituted non-C2 symmetric bisoxazoline diphenylamine ligand played pivotal role success chemistry, its distinct electronic steric effects proving crucial enhancing both reactivity stereoselectivity. Mechanistic studies supported idea that reaction underwent regioselective nucleophilic iodides, followed by radical alkynes. Notably, hydroxyl group generated from epoxide may play an auxiliary achieving high enantioselectivity.

Language: Английский

Citations

8

[3,3]‐Sigmatropic Rearrangements of Naphthyl 1‐Propargyl Ethers: para‐Propargylation and Catalytic Asymmetric Dearomatization DOI
Lifeng Wang, Yuqiao Zhou, Zhishan Su

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(52)

Published: Nov. 1, 2022

The para-Claisen rearrangement of aryl 1-propargyl ethers involves two-step [3,3]-sigmatropic rearrangements and dearomatization process, which has high activation barriers is challenge. Here we discovered thermal naphthyl ethers, it enabled the formation formal para-C-H propargylation products upon rearomatization. Chirality transfer occurred if optically active propargyl were employed, leading to construction aryl/propargyl-containing stereogenic centers. Moreover, catalytic asymmetric with different substitution at para-position gave access benzocyclohexenones bearing all-carbon quaternary stereocenters. reaction was accelerated by a chiral N,N'-dioxide/Co(OTf)2 complex catalyst achieve yields (up 98 %) enantioselectivities 93 % ee). DFT calculations experimental results provided important clues clarify process as well induction remote delivery.

Language: Английский

Citations

19

Copper Catalyzed Enantioconvergent Nucleophilic Substitutions DOI

Chunxi Huang,

Zilong Wan,

Aoping Zhu

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(10), P. 1161 - 1174

Published: Dec. 22, 2023

Comprehensive Summary As a versatile earth‐abundant transition metal, Cu has long been widely applied in the C—C and C—X bond forming reactions. for now, low‐valent Cu(I) is known to reduce redox active electrophiles via an SET pathway give corresponding radical Cu(II) species. The resulting species can interact with out‐sphere pathway, affording coupling product. Alternatively, trap through inner‐sphere process generate Cu(III) then realize challenging formations due facile reductive elimination of intermediate. Although copper catalysis arylations various nucleophiles, copper‐catalyzed enantioconvergent nucleophilic substitutions racemic alkyl have less explored, likely difficulties overcoming reduction potential electrophiles, side reactions, enantiomeric control. In order overcome high photo‐induced strategy developed under mild conditions. An alternative new anionic tridentate ligands also reported this regard. This review summarizes recent developments by nucleophiles C—N, C—C, C—B, C—P C—O their brief mechanistic studies. Key Scientists 2016, Fu Peters et al . first Cu‐catalyzed enantiocovergent C—N tertiary halides N ‐hetereocycles, opening door substitutions. that greatly enhances reducing power Cu(I). cyanation (decarboxylative) borylation were successively presented Liu Ito 2017 2018, respectively. Other than strategy, 2019 demonstrated significantly enhance ability cinchona‐based chiral utilized series Zhang containing oxazoline binding sites 2020. 2020, Xiao Lu al. deoxygenative cyanation. Later 2022, Feng guanidine hybrid ligands. focuses on emerged years.

Language: Английский

Citations

10

Photoinduced copper-catalyzed asymmetric cyanoalkylalkynylation of alkenes, terminal alkyne, and oximes DOI Creative Commons
Shuang Xin,

Jibang Liao,

Qi Tang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A properly designed chiral copper complex with a hybrid tridentate ligand enables photocatalytic asymmetric cyanoalkylalkynylation of olefins using cycloketone oxime esters as the precursors.

Language: Английский

Citations

4

Markovnikov Protoborylation of Unactivated Terminal Alkenes via Copper-Guanidine Catalysis DOI
Jin Tao, Yicen Ge, Ai Zhang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 23, 2025

Herein copper-catalyzed Markovnikov protoborylation of unactivated terminal alkenes was achieved through the employment a bulky σ-donating guanidine ligand. The reaction demonstrated good tolerance to diverse functional groups and remarkable selectivity for branched borylation products (86:14-97:3) under ambient conditions, which enabled synthesis secondary alkyl boronates in grams with further valuable derivatizations. Mechanistic studies suggested boryl insertion C═C bonds via Cu-guanidine complex ruled out possibility diboration-protodeboronation process.

Language: Английский

Citations

0

Dehydrative alkynylation of 3-hydroxyisoindolinones with terminal alkynes for the synthesis of 3-alkynylated 3,3-disubstituted isoindolinones DOI
Kai‐Cheng Yang,

Shi-Lu Zheng,

Zhong Wen

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(17), P. 3453 - 3458

Published: Jan. 1, 2024

A HOTf or Fe(OTf) 3 -catalyzed dehydrative alkynylation of 3-hydroxyisoindolinones with terminal alkynes was developed, which represents a brand-new procedure for the synthesis 3-alkynylated 3,3-disubstituted isoindolinones.

Language: Английский

Citations

2

Copper-catalyzed asymmetric dearomatizing amination of 2-naphthols: Csp2–N coupling via 1,3-reductive elimination DOI

Aying Yihuo,

Maoping Pu, Zheng Tan

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(8), P. 2694 - 2700

Published: July 2, 2024

Language: Английский

Citations

2

Asymmetric synthesis of cyclopenta[b]indoles via organocatalytic formal (3 + 2) cyclization of β-keto ester with azonaphthalene DOI

Yanji Song,

Shi Tang,

Qianping Chen

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2734 - 2739

Published: Jan. 1, 2023

Enantioselective formal (3 + 2) cyclization of cyclic β-keto esters with azonaphthalenes to synthesize cyclopenta[ b ]indoles in good yields high diastereo- and enantioselectivity is established by using guanidine-amides as catalysts under mild reaction conditions.

Language: Английский

Citations

4

Asymmetric [3+2]-cyclization of α-imino amide surrogates to construct 3,4-diaminopyrrolidine-2,5-diones DOI
Peiran Ruan,

Cefei Zhang,

Wu Jin

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(53), P. 8250 - 8253

Published: Jan. 1, 2023

Using newly designed α-imino amide surrogates and azlactones as amphiphilic reactants, catalyzed by a chiral bifunctional guanidine, the construction of 3,4-diaminopyrrolidine-2,5-diones their derivatives was realized via formal [3+2]-cyclization. The role guanidine multiple hydrogen bond donor demonstrated DFT calculations.

Language: Английский

Citations

4