Cu(I)-Catalyzed Cross-Coupling of Terminal Alkynes with Trifluoromethyl Ketone <i>N</i>-Tosylhydrazones: Access to 1,1-Difluoro-1,3-enynes

Zhang, Zhikun; Zhou, Qi; Yu, Weizhi; Li, Tianjiao; Wu, Guojiao; Zhang, Yan; Wang, Jianbo

doi:10.1021/acs.orglett.5b00980

Cited by 129 publications

(50 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Wang first reported the reaction of arylboronic acids with 2,2,2‐trifluorodiazoethane under transition‐metal free conditions to access 1,1‐difluoroalkenes . In 2015, the same group developed the Cu I ‐catalysed cross‐coupling of terminal alkynes 22 with trifluoromethyl containing N ‐tosylhydrazones 23 giving access to a wide range of 1,1‐difluoro‐1,3‐enynes 24 (Scheme ) . The reaction is proposed to proceed via a copper‐carbene complex 26 obtained via dediazoniation of the CF 3 ‐diazo precursor with copper‐alkynyl complex 25 .…”

Section: Transition‐metal Catalysismentioning

confidence: 99%

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

Jaroschik

2018

Chemistry A European J

147

View full text Add to dashboard Cite

The introduction of a trifluoromethyl (CF ) group into an organic molecule can modify its chemical behavior and lead to changes in its physicochemical and pharmacological properties. The CF group is often chosen for its chemical inertness and stability, which are related to the strong C-F bonds. In recent years, the potential of gaining straightforward access to difluorinated compounds through selective single C-F activation in CF groups has been unveiled. This review describes the latest methodologies for the synthesis of difluoromethylated arenes, difluoroalkenes and difluorinated aldol products of potential synthetic and/or biological interest, employing low-valent metals, transition metal catalysis, FLP and Lewis acid mediated transformations as well as photoredox catalysis.

show abstract

Section: Transition‐metal Catalysismentioning

confidence: 99%

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

Jaroschik

2018

Chemistry A European J

147

View full text Add to dashboard Cite

show abstract

“…1,1-difluoro-1,3-enynes were accessed in a process that involved a rare β-F elimination (Scheme 13, b). 17…”

Section: Scheme 12mentioning

confidence: 99%

The rich reactivity of transition metal carbenes with alkynes

Torres

Pla‐Quintana

2016

Tetrahedron Letters

View full text Add to dashboard Cite

Transition metal carbenes are versatile intermediates that can mediate many reactions. Among the different reactions they can participate in, their reactions with alkynes are especially diverse. The present digest describes the different reaction pathways that can take place when a transition metal carbene reacts with an alkyne, summarizes the most recent developments for each reactivity profile, and tries to shed light on the factors influencing the different reaction typesWe gratefully acknowledge the financial support of our own research in this area by the Spanish Ministry of Education and Science (MINECO) (Project CTQ2014-54306-P) and the DIUE of the Generalitat de Catalunya (Project 2014-SGR-931 and FI predoctoral grant to Ò.T.

show abstract

“…Wang and co-workers reported the Cu I -catalyzed coupling of trifluoromethyl ketone hydrazones with alkynes by the migratory insertion of copper carbene intermediates followed by b-fluorine elimination from the generated a-CF 3 alkylcopper species (Scheme 25). [56] In this reaction, aC F 3 group is located on the carbene carbon atom, whereas aC F 3 group serves as am igrative moiety in the study by Hu and coworkers on Cu I -catalyzed difluoromethylenation (Scheme 24). [55] Similarly,the Au I -catalyzed coupling of diazo compounds with fluorinated enol silyl ethers proceeds through gold carbene complexes,a sr eported by Zhou and co-workers (Scheme 26).…”

Section: Migratory Insertionmentioning

confidence: 99%

Transition‐Metal‐Mediated and ‐Catalyzed C−F Bond Activation by Fluorine Elimination

2018

View full text Add to dashboard Cite

The activation of carbon-fluorine (C-F) bonds is an important topic in synthetic organic chemistry. Metal-mediated and -catalyzed elimination of β- or α-fluorine proceeds under milder conditions than oxidative addition to C-F bonds. The β- or α-fluorine elimination is initiated from organometallic intermediates having fluorine substituents on carbon atoms β or α to metal centers, respectively. Transformations through these elimination processes (C-F bond cleavage), which are typically preceded by carbon-carbon (or carbon-heteroatom) bond formation, have been increasingly developed in the past five years as C-F bond activation methods. In this Minireview, we summarize the applications of transition-metal-mediated and -catalyzed fluorine elimination to synthetic organic chemistry from a historical perspective with early studies and from a systematic perspective with recent studies.

show abstract

Cu(I)-Catalyzed Cross-Coupling of Terminal Alkynes with Trifluoromethyl Ketone N-Tosylhydrazones: Access to 1,1-Difluoro-1,3-enynes

Cited by 129 publications

References 54 publications

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

The rich reactivity of transition metal carbenes with alkynes

Transition‐Metal‐Mediated and ‐Catalyzed C−F Bond Activation by Fluorine Elimination

Contact Info

Product

Resources

About