Density Functional Theory Study on the Mechanism of Organophosphine-Catalyzed [4+2] Cycloaddition Reaction DOI Open Access
Zheng Li,

Yingchun Gu,

Da‐Zhen Xu

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 42(3), P. 830 - 830

Published: Jan. 1, 2022

费学宁 a 张 磊 * ,a ( 天津城建大学理学院 天津 300384) b 南开大学化学学院 农药国家工程研究中心 300071) 摘要 有机膦催化的环加成反应是构建重要杂环骨架的高效方法, 从文献报道中选取一个膦催化共轭二烯与 α,β-不饱 和酮的[4+2]环加成反应为研究对象, 通过密度泛函理论计算、表征反应的详细机制. 总反应包含的四个基元步骤依次 为偶极离子形成、分子间亲核加成、分子内环化和膦配体解离.活化自由能垒的计算值为 84.4 kJ/mol, 总反应的自由能 变的计算值为-18.8kJ/mol.当使用手性膦催化剂时, 计算出的反应机理和动力学参数与实验观测的对映异构选择性 相符, 并且揭示了立体选择性的根源是空间位阻导致过渡态的扭转张力增大, 从而不利于次要对映异构体的形成.最 后, 设计了四种二烯底物, 分别考察了它们与膦催化剂形成的偶极离子中间体, 表明底物上的 2-酯基对反应活性和位 置选择性起至关重要的影响, 而 1-酯基的作用可能不重要.研究成果可以为优化实验条件和设计新反应提供理论指导.

Copper-decorated covalent organic framework as a heterogeneous photocatalyst for phosphorylation of terminal alkynes DOI
Yuxuan Chen, Mo Zhang, Shuai‐Zheng Zhang

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(10), P. 4071 - 4081

Published: Jan. 1, 2022

A copper decorated covalent organic framework has been prepared and identified as an efficient heterogeneous photocatalyst for the phosphorylation of terminal alkynes.

Language: Английский

Citations

74

A H4SiW12O40-catalyzed three-component tandem reaction for the synthesis of 3,3-disubstituted isoindolinones DOI
Yufeng Liu,

Guodong Zeng,

Yutao Cheng

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(1), P. 108480 - 108480

Published: April 20, 2023

Language: Английский

Citations

29

Chiral Bisphosphine-Catalyzed Asymmetric Staudinger/aza-Wittig Reaction: An Enantioselective Desymmetrizing Approach to Crinine-Type Amaryllidaceae Alkaloids DOI
Hongzhi Yang, Jingyang Zhang, Sen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 14136 - 14148

Published: April 20, 2024

An unprecedented chiral bisphosphine-catalyzed asymmetric Staudinger/aza-Wittig reaction of 2,2-disubstituted cyclohexane-1,3-diones is reported, enabling the facile access a broad range cis-3a-arylhydroindoles in high yields with excellent enantioselectivities. The key to success this work relies on first application bisphosphine DuanPhos reaction. effective reductive system has been established address challenging PV═O/PIII redox cycle associated catalyst. In addition, comprehensive experimental and computational investigations were carried out elucidate mechanism Leveraging newly developed chemistry, enantioselective total syntheses several crinine-type Amaryllidaceae alkaloids, including (+)-powelline, (+)-buphanamine, (+)-vittatine, (+)-crinane, have accomplished remarkable conciseness efficiency.

Language: Английский

Citations

7

Organophosphorus-Catalyzed Direct Dehydroxylative Thioetherification of Alcohols with Hypervalent Organosulfur Compounds DOI
Gang Sun, Shiping Zhan,

Yi-Feng Zhao

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(2), P. 1083 - 1090

Published: Jan. 4, 2024

A metal-free and thiol-free organophosphorus-catalyzed method for forming thioethers was disclosed, driven by PIII/PV═O redox cycling. In this work, one-step dehydroxylative thioetherification of alcohols fulfilled with various hypervalent organosulfur compounds. This established strategy features an excellent functional group tolerance broad substrate scope, especially inactivated alcohols. The scale-up reaction further transformation the product were also successful. Additionally, offers a protecting-group-free step-efficient approach synthesizing peroxisome proliferator-activated receptor agonists which exhibited promising potential treating osteoporosis in mammals.

Language: Английский

Citations

4

PIII/PV═O Redox Catalysis Mediated Thioesterification of Carboxylic Acids with Disulfides under Air Conditions DOI
Gang Sun,

Yi-Feng Zhao,

Yi-Han Yu

et al.

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

Published: Jan. 12, 2025

An efficient organophosphorus-catalyzed thiocarbonylation reaction of disulfides with carboxylic acids under air conditions was described. Various functional groups on and can be tolerated the present conditions, affording thioesters in good to excellent yields. This method exhibited chemoselectivity applied for late-stage functionalization drug molecules containing a acid group.

Language: Английский

Citations

0

The Outstanding Ambiphilicity of Trialkylstibines among Trialkylpnictines: Power for Stepwise Deoxygenation and N–N Coupling of Nitroarenes DOI
Zichen Zhang, Kunlong Li, Minghao Huang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 12, 2025

The ongoing discovery of highly reactive ambiphilic main-group species has significantly advanced the development chemistry, particularly in realms small molecule activation and catalysis. Theoretically, compounds featuring smaller HOMO–LUMO gaps gain stronger ambiphilicity higher reactivity. In this work, we fundamentally demonstrate that Me3Sb holds smallest gap among trimethylpnictines, indicating its outstanding ambiphilicity. Correspondingly, superior reactivity toward deoxygenation electron-deficient nitroarenes been unambiguously revealed through control experiments. Furthermore, unprecedented SbIII/SbVO cycling between trialkylstibines their oxides established for catalytic transformation into azoxyarenes/azoarenes. This study opens a new chapter organoantimony derivatives fields redox

Language: Английский

Citations

0

Visible-Light-Initiated Multicomponent Reactions of α-Diazoesters to Access Organophosphorus Compounds DOI

Chengming Qu,

Jindong Hao,

Hongyu Ding

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(19), P. 12921 - 12931

Published: Sept. 21, 2022

A simple visible-light-initiated strategy has been established for the construction of organophosphorus compounds via aerobic multicomponent reaction α-diazoesters, cyclic ethers, and P(O)H under air. number phosphonates phosphinates could be efficiently isolated in moderate to good yields without use photosensitizers metal reagents. This advantages mild condition, operation, eco-friendly energy, functional-group tolerance, gram-scale synthesis.

Language: Английский

Citations

16

Copper-Catalyzed Phosphorylation of N,N-Disubstituted Hydrazines: Synthesis of Multisubstituted Phosphorylhydrazides as Potential Anticancer Agents DOI
Lvyin Zheng,

Liuhuan Cai,

Weijie Mei

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(9), P. 6224 - 6236

Published: April 20, 2022

An efficient copper-catalyzed aerobic oxidative cross-dehydrogenative coupling reaction for the synthesis of multisubstituted phosphorylhydrazides from N,N-disubstituted hydrazines and hydrogen phosphoryl compounds is accomplished. The proceeds under mild conditions without addition any external oxidants bases. This work reported here represents a direct P(═O)-N-N bond formation with advantages being operationally simple, good functional group tolerance, high atom step economy. Furthermore, selected exhibit potential inhibitory activity against tumor cells, which can be used in field screening anticancer agents as new chemical entities.

Language: Английский

Citations

15

Antimony Redox Catalysis: Hydroboration of Disulfides through Unique Sb(I)/Sb(III) Redox Cycling DOI
Minghao Huang, Kunlong Li, Zichen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20432 - 20438

Published: July 9, 2024

The stibinidene ArSb

Language: Английский

Citations

3

Organophosphorus-Catalyzed “Dual-Substrate Deoxygenation” Strategy for C–S Bond Formation from Sulfonyl Chlorides and Alcohols/Acids DOI
Gang Sun, Jing Li, Xin Liu

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 8628 - 8635

Published: June 9, 2023

A green method to construct C-S bonds using sulfonyl chlorides and alcohols/acids via a PIII/PV═O catalytic system is reported. The organophosphorus-catalyzed umpolung reaction promotes us propose the "dual-substrate deoxygenation" strategy. Herein, we adopt strategy, which achieves deoxygenation of synthesize thioethers/thioesters driven by redox cycling. represents an operationally simple approach stable phosphine oxide as precatalyst shows broad functional group tolerance. potential application this protocol demonstrated late-stage diversification drug analogues.

Language: Английский

Citations

8