Transition Metal‐Controlled Direct Regioselective Intermolecular Amidation of C−H Bonds with Azodicarboxylates: Scope, Mechanistic Studies, and Applications

2018 ◽  
Vol 360 (21) ◽  
pp. 4205-4214 ◽  
Author(s):  
He‐Yuan Bai ◽  
Xin Fu ◽  
Jin‐Long Pan ◽  
Hai‐Qian Ma ◽  
Zhi‐Min Chen ◽  
...  
Keyword(s):  
Transition Metal ◽  
Mechanistic Studies

scholarly journals Transition-Metal-Free Boryl Substitution Using Silylboranes and Alkoxy Bases

Synlett ◽  
2017 ◽  
Vol 28 (11) ◽  
pp. 1258-1267 ◽  
Author(s):  
Hajime Ito ◽  
Eiji Yamamoto ◽  
Satoshi Maeda ◽  
Tetsuya Taketsugu
Keyword(s):  
Transition Metal ◽  
Functional Group ◽  
Experimental Studies ◽  
Transition Metal Catalysts ◽  
Alkyl Halides ◽  
Aryl Halides ◽  
Nucleophilic Attack ◽  
Important Class ◽  
Mechanistic Studies ◽  
Induced Reaction

Silylboranes are used as borylation reagents for organohalides in the presence of alkoxy bases without transition-metal catalysts. PhMe2Si–B(pin) reacts with a variety of aryl, alkenyl, and alkyl halides, including sterically hindered examples, to provide the corresponding organoboronates in good yields with high borylation/silylation ratios, showing good functional group compatibility. Halogenophilic attack of a silyl nucleophile on organohalides, and subsequent nucleophilic attack on the boron electrophile are identified to be crucial, based on the results of extensive theoretical and experimental studies. This boryl­ation reaction is further applied to the first direct dimesitylboryl (BMes2) substitution of aryl halides using Ph2MeSi–BMes2 and Na(O-t-Bu), affording aryldimesitylboranes, which are regarded as an important class of compounds for organic materials.1 Introduction2 Boryl Substitution of Organohalides with PhMe2Si–B(pin)/Alkoxy Bases3 Mechanistic Investigations4 DFT Mechanistic Studies Using an Artificial Force Induced Reaction (AFIR) Method5 Dimesitylboryl Substitution of Aryl Halides with Ph2MeSi–BMes2/Na(O-t-Bu)6 Conclusion

Rongalite-Induced Transition-Metal and Hydride-Free Reductive Aldol Reaction: A Rapid access to 3,3´- Disubstituted Oxindoles and Its Mechanistic Studies

2022 ◽  
Author(s):  
Sivaparwathi Golla ◽  
Naveenkumar Anugu ◽  
Swathi Jalagam ◽  
Hari Prasad Kokatla
Keyword(s):  
Transition Metal ◽  
Aldol Reaction ◽  
Dual Role ◽  
Biologically Active ◽  
Mechanistic Studies ◽  
Rapid Access ◽  
Reductive Aldol ◽  
Isatin Derivatives

A transition-metal and hydride-free reductive aldol reaction has been developed for the synthesis of biologically active 3,3´-disubstituted oxindoles from isatin-derivatives using rongalite. In this protocol, rongalite plays the dual role...

scholarly journals Boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides with silylborane and an alkoxy base: expanded scope and mechanistic studies

2015 ◽  
Vol 6 (5) ◽  
pp. 2943-2951 ◽  
Author(s):  
Eiji Yamamoto ◽  
Satoshi Ukigai ◽  
Hajime Ito
Keyword(s):  
Transition Metal ◽  
Mechanistic Studies ◽  
Metal Free

A transition-metal-free method has been developed for the boryl substitution of functionalized aryl-, heteroaryl- and alkenyl halides using a silylborane/alkoxy-base reagent. Borylation of (Z)-alkenyl halides proceeded in a stereoretentive manner.

Deuterated Aryl Alkyl Ethers Synthesis via Nucleophilic Etherification of Aryl Alkyl Ethers and Thioethers with Deuterated Alcohols

Synlett ◽  
2019 ◽  
Vol 30 (15) ◽  
pp. 1805-1809
Author(s):  
Shuai Li ◽  
Xia Wang ◽  
Xin-Ge Yang ◽  
Gui-Quan Yu ◽  
Xue-Qiang Wang
Keyword(s):  
Transition Metal ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Metal Free ◽  
Wide Range ◽  
Alkyl Ethers

A transition-metal-free etherification protocol that is capable of synthesizing deuterated ethers is described. A wide range of aryl alkyl ethers and thioethers were suitable for this transformation owing to the mild reaction conditions. Besides, a series of sterically bulky deuterated alcohols were successfully incorporated into cyano-substituted arenes. The results of mechanistic studies suggested this reaction might take place via nucleophilic aromatic substitution pathway.

Metal-Free Catalytic Aromatic C–H Borylation

Synlett ◽  
2020 ◽  
Vol 31 (19) ◽  
pp. 1857-1861
Author(s):  
Hua Zhang ◽  
Li Wang
Keyword(s):  
Transition Metal ◽  
Recent Progress ◽  
Rapid Development ◽  
Transition Metal Catalysis ◽  
Mechanistic Studies ◽  
Metal Catalysis ◽  
Promising Alternative ◽  
Metal Free ◽  
History Of ◽  
Near Future

In recent decades, C–H borylation has undergone rapid development and has become one of the most important and efficient methods for the synthesis of organoboron compounds. Although transition-metal catalysis dominates C–H borylation, the metal-free approach has emerged as a promising alternative strategy. This article briefly summarizes the history of metal-free aromatic C–H borylation, including early reports on electrophilic C–H borylation and recent progress in metal-free catalytic intermolecular C–H borylation; it also highlights our recent work on BF3·Et2O-catalyzed C2–H borylation of hetarenes. Despite these recent advances, comprehensive mechanistic studies on various metal-free catalytic aromatic C–H borylations and novel processes with a wider substrate scope are eagerly expected in the near future.

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