gem-Difluorinated Cyclopropanes for α-Fluoro-allylation of Enantioselective Amino Acid Esters DOI
Hisashi Yamamoto, Abhijit Paul

Synfacts, Journal Year: 2024, Volume and Issue: 20(06), P. 0661 - 0661

Published: May 14, 2024

Key words α-fluoroallylation - synergistic relay catalysis Tsuji–Trost reaction α-quaternary α-amino acid

Language: Английский

Observation of unusual outer-sphere mechanism using simple alkenes as nucleophiles in allylation chemistry DOI Creative Commons
Yaxin Zeng, Han Gao, Zhong‐Tao Jiang

et al.

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

Published: May 21, 2024

Abstract Transition-metal catalyzed allylic substitution reactions of alkenes are among the most efficient methods for synthesizing diene compounds, driven by inherent preference an inner-sphere mechanism. Here, we present a demonstration outer-sphere mechanism in Rh-catalyzed reaction simple using gem -difluorinated cyclopropanes as allyl surrogates. This unconventional offers opportunity fluorine recycling via C − F bond cleavage/reformation, ultimately delivering carbofluorination products. The developed method tolerates wide range alkenes, providing access to secondary, tertiary fluorides and -difluorides with 100% atom economy. DFT calculations reveal that formation goes through unusual nucleophilic allyl-Rh species instead migration insertion, generated carbon cation then forms tetrafluoroborate fluoride shuttle.

Language: Английский

Citations

9
Palladium/Amine Dual-Catalyzed Tsuji–Trost Fluoroallylation of Aldehydes with gem-Difluorinated Cyclopropanes DOI
Zhengquan Su,

Binhong Tan,

Zhaodong Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(25), P. 5375 - 5379

Published: June 12, 2024

We herein disclose the Pd/amine dual-catalyzed ring-opening cross-coupling reaction between

Language: Английский

Citations

5
Synergistic Pd/Ni Dual-Catalyzed Cross-Coupling of Azaaryl Acetates with gem-Difluorinated Cyclopropanes DOI
Xuexue Zhang,

H. HELEN LIN,

Binhong Tan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(41), P. 8956 - 8960

Published: Oct. 7, 2024

We herein report the development of a novel Pd/Ni dual-catalyzed ring-opening functionalization

Language: Английский

Citations

5
Palladium-Catalyzed Dearomative Fluoroallylation of Pyrroles with gem-Difluorinated Cyclopropanes DOI
Long Gu, Fajie Duan,

Jiafeng Ye

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

We herein report the development of a novel Pd-catalyzed dearomative functionalization pyrroles with gem-difluorinated cyclopropanes (gem-F2CPs). This dearomative/ring-opening strategy streamlines diversity-oriented synthesis (DOS) α-quaternary 2-fluoroallylic 2H-pyrroles broad scope and excellent functional group tolerance, which enables efficient late-stage transformation complex bioactive molecule-derived gem-F2CPs. Derivation resulting fluoroallylic to different synthetically useful 2H-pyrrole motifs demonstrated synthetic value this methodology.

Language: Английский

Citations

0
Palladium-Catalyzed Ring-Opening Defluorinative Hiyama Cross-Coupling of gem-Difluorocyclopropanes with Arylsilanes DOI

Zimin Wang,

Daniel C. Hong,

Hongfang Li

et al.

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

Published: April 18, 2025

We report an efficient palladium-catalyzed ring-opening defluorinative Hiyama cross-coupling of gem-difluorocyclopropanes with structurally diverse (hetero)arylsilanes through C-C bond activation and C-F cleavage. This regioselective features a broad substrate scope excellent functional group compatibility, affording variety linear 2-fluoroallylic scaffolds in good yields high Z-selectivity.

Language: Английский

Citations

0
Direct Enantioselective Allylic Alkylation of α-Amino Esters to Quaternary Glutamates via Strategic Pyridoxal Catalyst Design DOI
Zhengjun Shi, Tianhao Wu,

Longjie Huang

et al.

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

Published: April 24, 2025

The difficulty for N-unprotected α-substituted glycinates as α-C nucleophiles originates from both competing N nucleophilic interference and steric hindrance of the α substituent, which makes direct asymmetric alkylation with Morita-Baylis-Hillman (MBH) adducts especially challenging. Given wide utilization α-quaternary chiral glutamic acid derivatives in therapeutic studies, we took advantage biomimetic carbonyl catalysis to achieve their efficient synthesis. A bifunctional centrally pyridoxal, featured an expanded catalytic cavity reduced around aldehyde group, was designed synthesized. In this work, describe novel pyridoxal enabled MBH acetates. broad range multiple modifications were produced high reactivity excellent stereocontrol.

Language: Английский

Citations

0
Asymmetric bifunctionalization of allenes with aryl iodides and amino acids enabled by chiral aldehyde/palladium combined catalysis DOI Creative Commons
Hao Zhang, Wen Wei, Yuyang Wang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(32), P. 12983 - 12988

Published: Jan. 1, 2024

An asymmetric bifunctionalization of allenes with aryl/alkenyl iodides and amino acid esters is achieved under the promotion chiral aldehyde/palladium combined catalysis.

Language: Английский

Citations

3
Pd-IPent-Catalyzed Defluorinative Annulation of gem-Difluorocyclopropanes with Enamides: Synthesis of Multisubstituted N-H Pyrroles DOI
Wenhao Liu,

Yahui Ma,

Qiuwei Huang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

We present a Pd-IPent-catalyzed ring-opening defluorinative annulation reaction of gem-difluorocyclopropanes with enamides, which provides convenient and efficient strategy for the synthesis multisubstituted N-H pyrrole derivatives. This transformation selectively cleaves C1-C3 bond, two C-F bonds, C-N bond in one-pot procedure. Additionally, this protocol allows modification several bioactive molecules.

Language: Английский

Citations

0
Asymmetric α-Allylation of Amino Acid Esters with Alkynes Enabled by Chiral Aldehyde/Palladium Combined Catalysis DOI

Yao Lin,

Wen Wei, Jianhua Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(37), P. 7908 - 7913

Published: Sept. 10, 2024

A highly efficient, atom-economical α-allylation reaction of NH

Language: Английский

Citations

1
Palladium(II)-Catalyzed Enantioselective Ring Opening of Oxabenzonorbornadienes via Domino Aminopalladation of Alkynylanilines DOI
Qianru Liu,

Junjie Meng,

Binhong Tan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 27(1), P. 369 - 375

Published: Dec. 30, 2024

We report herein a robust enantioselective ring opening coupling of oxabenzonorbornadienes via Pd(II)-catalyzed domino cyclization alkynylanilines, which features the formation three covalent bonds and two contiguous stereocenters with excellent enantio- diastereoselectivity broad substrate scope. The good functional group tolerance this desymmetrization strategy enables efficient late-stage transformation natural product-derived alkynylanilines. resulting indolated dihydronaphthols could serve as valuable platform to streamline diversity-oriented synthesis other enantioenriched tetrahydronaphthalene derivatives.

Language: Английский

Citations

1