Borane-catalyzed arylation of aryldiazoacetates with<i>N</i>,<i>N</i>-dialkylanilines

Chen, Cheng-Yu; Zhao, Jing‐Hao; Xiong, Li-Xue; Wang, Feiyi; Yang, Guichun; Ma, Chao

doi:10.1039/d2ob00447j

“…Finally, borane‐catalyzed C−H insertion of 3 with 2‐phenyl diazoacetate provided 162 in 58 % yield with moderate stereoselectivity (1 : 1 d.r. ), [63] while the selective C−H arylation of 16 with boronic acid produced the 5‐aryl‐1,2‐dihydropyrimidine 164 in 72 % yield [64] . Furthermore, product 70 undergoes selective C−H phosphinylation [65] with dimethyl phosphite or diphenylphosphine oxide to furnish products 167 and 168 in 68 % and 97 % yield, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…[62] Finally, borane-catalyzed CÀ H insertion of 3 with 2-phenyl diazoacetate provided 162 in 58 % yield with moderate stereoselectivity (1 : 1 d.r. ), [63] while the selective CÀ H arylation of 16 with boronic acid produced the 5-aryl-1,2-dihydropyrimidine 164 in 72 %…”

Section: Methodsmentioning

confidence: 99%

Dearomative Insertion of Fluoroalkyl Carbenes into Azoles Leading to Fluoroalkyl Heterocycles with a Quaternary Center

Li,

Ning,

Chen

et al. 2023

View full text Add to dashboard Cite

The skeletal ring expansion of heteroarenes through carbene insertion is gaining popularity in synthetic chemistry. Efficient strategies for heterocyclic ring expansion to access heterocycles containing a fluoroalkyl quaternary carbon center through fluoroalkyl carbene insertion are highly desirable because of their broad applications in medicinal chemistry. Here, we report a general strategy for the dearomative one‐carbon insertion of azoles using fluoroalkyl N‐triftosylhydrazones as fluoroalkyl carbene precursors, resulting in ring‐expanded heterocycles in excellent yields and good functional group compatibility. The broad generality of this methodology in the late‐stage diversification of pharmaceutically interesting bioactive molecules and versatile transformations of the products has been demonstrated.

show abstract

“…[62] Finally, borane-catalyzed CÀ H insertion of 3 with 2-phenyl diazoacetate provided 162 in 58 % yield with moderate stereoselectivity (1 : 1 d.r. ), [63] while the selective CÀ H arylation of 16 with boronic acid produced the 5-aryl-1,2-dihydropyrimidine 164 in 72 % yield. [64] Furthermore, product 70 undergoes selective CÀ H phosphinylation [65] with dimethyl phosphite or diphenylphosphine oxide to furnish products 167 and 168 in 68 % and 97 % yield, respectively.…”

Section: Resultsmentioning

confidence: 99%

Dearomative Insertion of Fluoroalkyl Carbenes into Azoles Leading to Fluoroalkyl Heterocycles with a Quaternary Center

Li,

Ning,

Chen

et al. 2023

Angewandte Chemie

0

View full text Add to dashboard Cite

The skeletal ring expansion of heteroarenes through carbene insertion is gaining popularity in synthetic chemistry. Efficient strategies for heterocyclic ring expansion to access heterocycles containing a fluoroalkyl quaternary carbon center through fluoroalkyl carbene insertion are highly desirable because of their broad applications in medicinal chemistry. Here, we report a general strategy for the dearomative one‐carbon insertion of azoles using fluoroalkyl N‐triftosylhydrazones as fluoroalkyl carbene precursors, resulting in ring‐expanded heterocycles in excellent yields and good functional group compatibility. The broad generality of this methodology in the late‐stage diversification of pharmaceutically interesting bioactive molecules and versatile transformations of the products has been demonstrated.

show abstract

Borane‐Catalyzed, HFIP‐Assisted Carbene Insertion into Internal Alkenyl C−H Bonds under Metal‐Free Conditions

Huang

¹

,

Lin

²

,

Ma

³

et al. 2022

Adv Synth Catal

1

0

View full text Add to dashboard Cite

Carbene insertion into the C(sp2)−H bonds of internal alkenes was enabled in air by HFIP (1,1,1,3,3,3‐hexafluoro‐2‐propanol) as both the mediator and solvent through its cooperation with borane B(C6F5)3 as the catalyst. 3‐Diazooxindoles and 3‐diazoindolin‐2‐imines were amenable to work as the carbene precursors, and α‐oxo ketene dithioacetals acted as the internal alkenes at ambient temperature. The present synthetic protocol features metal‐free conditions, diverse substituent tolerance, and 47–84% yields, offering an efficient route to 3‐vinylated oxindole and indole derivatives.

show abstract

Borane-catalyzed arylation of aryldiazoacetates withN,N-dialkylanilines

Abstract: A selective arylation of donor-acceptor diazo compounds with aniline derivatives catalyzed by Lewis acidic boranes is developed. This simple reaction protocol provides an efficient method for the synthesis of diarylacetates...

Cited by 6 publications

References 79 publications

Dearomative Insertion of Fluoroalkyl Carbenes into Azoles Leading to Fluoroalkyl Heterocycles with a Quaternary Center

Dearomative Insertion of Fluoroalkyl Carbenes into Azoles Leading to Fluoroalkyl Heterocycles with a Quaternary Center

Dearomative Insertion of Fluoroalkyl Carbenes into Azoles Leading to Fluoroalkyl Heterocycles with a Quaternary Center

Borane‐Catalyzed, HFIP‐Assisted Carbene Insertion into Internal Alkenyl C−H Bonds under Metal‐Free Conditions

Contact Info

Product

Resources

About