Article
Chemistry, Organic
Regina M. Oechsner, Ivo H. Lindenmaier, Ivana Fleischer
Summary: We present a nickel catalyzed C-S cross-coupling reaction of aryl and alkenyl triflates with alkyl thiols. By using an air-stable nickel precatalyst, various thioethers could be synthesized under mild reaction conditions within a short reaction time. The reaction demonstrated a broad substrate scope, including pharmaceutically relevant compounds.
Article
Chemistry, Multidisciplinary
Yonggang Jiang, Bijun Wang, Dongxiang Liu, Dazhen Xia, Zhengfen Liu, Liang Li, Guogang Deng, Xiaodong Yang
Summary: In this study, an efficient method for synthesizing aryl acrylonitrile derivatives was developed using a Palladium/NIXANTPHOS-based catalyst system. The method demonstrated high yields and synthetic versatility for various substitutions and functionalizations.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Organic
Lu Lei, Pei-Sen Zou, Zhi-Xin Wang, Cui Liang, Cheng Hou, Dong-Liang Mo
Summary: A regioselective Heck reaction catalyzed by a P-containing palladacycle was described, which affords 2-aryl-2,5-dihydrofurans and 2-aryl-2,3-dihydrofurans in good yields from 2,3-dihydrofuran with diaryliodonium salts and aryl iodides, respectively. Mechanistic studies and DFT calculations revealed the chemoselectivity and regioselectivity-determining step of this reaction.
Article
Chemistry, Multidisciplinary
Xiang Li, Gao-Wei Wang, Li-Xia Liu, Chang-Bin Yu, Yong-Gui Zhou
Summary: Here, the authors describe the first example of palladium-catalyzed asymmetric hydrogenolysis of easily accessible aryl triflates for the construction of axially chiral biaryl scaffolds. The resulting chiral biaryl compounds were used to prepare axially chiral monophosphine ligands, which were further employed in palladium-catalyzed asymmetric allylic alkylation with excellent enantioselectivities and high branched and linear ratios, highlighting the potential utility of this methodology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Dan Li, Li Wei, Chaorong Qi, Wenfang Xiong, Hongjian Liu, Huanfeng Jiang
Summary: A palladium-catalyzed direct carbonylation of aryl bromides with carbon dioxide as the carbonyl source has been developed, providing an efficient route to a variety of aryl carboxylic acids in moderate to high yields. The method has many advantages including the use of a simple palladium catalyst system, wide substrate scope, good functional group tolerance, high yields, and easy scalability.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Li Gong, Chao Li, Fangyan Yuan, Senlin Liu, Xiaoming Zeng
Summary: The use of chromium catalysis enables the borylation of vinyl triflates and aryl carboxylic esters with pinacolborane by selectively forming vinyl and aryl boronate esters. Mechanistic studies suggest that either Sigma-bond metathesis or oxidative addition mechanisms are responsible for cleaving the ester scaffolds.
Article
Chemistry, Organic
Qingyuan Feng, Yuanyuan Fu, Yu Zheng, Saihu Liao, Shenlin Huang
Summary: Versatile beta-keto sulfonyl fluorides can be synthesized by electrochemical methods using inexpensive graphite felt as electrodes, without the need for metal catalysts. This protocol offers a mild and scalable approach to access valuable compounds from readily available precursors, including cyclic ones that were previously difficult to obtain.
Article
Chemistry, Organic
Baptiste Picard, Takahide Fukuyama, Ilhyong Ryu
Summary: An improved carbonylation method for amide bond formation between aryl iodides and aromatic amines is presented, which does not require a phosphine ligand unlike conventional Pd catalysis. The catalyst system consists of bis(dibenzylideneacetone)palladium (0.5 mol %) and DBU (10 mol %). This method allows the synthesis of various aromatic amides and can be scaled to gram order synthesis under low carbon monoxide pressure.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Dan Li, Li Wei, Wenfang Xiong, Huanfeng Jiang, Chaorong Qi
Summary: A palladium-catalyzed reductive formylation of aryl iodides with carbon dioxide as the carbonyl source was achieved using Pd(PCy3)2Cl2 and di-2-pyridyl ketone as the catalyst and phenylsilane as the reductive reagent under mild reaction conditions. The reaction provided a variety of aromatic aldehydes in moderate to excellent yields and exhibited good substrate scope, functional group tolerance, and easy operation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Peizhuo Lv, Ali Wang, Xin Xie, Yulong Chen, Yuanhong Liu
Summary: An efficient method for the coupling of allyl trifluoroborates with aryl halides has been developed. The method offers high efficiency, mild reaction conditions, wide substrate scope, and functional group compatibility. Mechanistic studies suggest the formation of a pi-allyl nickel(III) intermediate as a key reaction intermediate.
Article
Chemistry, Organic
Ninglin Li, Fuqiang Xiong, Ke Gao
Summary: An efficient cobalt-based catalytic system has been developed for the protodeboronation of various aryl and vinyl boronates, tolerating a wide range of functional groups. Additionally, the reaction has been extended to deuterodeboronation with D2O, offering a potential protocol for the synthesis of regiospecifically deuterated arenes and olefins.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Pierre-Louis Lagueux-Tremblay, Celestin Augereau, Pranav Nair, Kwan Ming Tam, Bruce A. Arndtsen
Summary: The use of metal catalysis to form potent acylating agents is an important approach to expand the application of carbonylation reactions. However, the reductive elimination of these reactive products has been a challenge, making these reactions often high temperature, high pressure, and limited in scope. In this study, a mild and versatile palladium catalyzed carbonylative method was developed to generate electrophilic acyl-DMAP salts by exploiting the counterion. The weakly coordinating triflate anion was found to destabilize Pd(II) and enable irreversible reductive elimination, while ligand design facilitated the rapid activation of aryl or vinyl triflates. This approach allows palladium catalyzed carbonylations to be carried out under exceptionally mild conditions, with low catalyst loading and using readily available C(sp2)-triflate reagents.
Article
Chemistry, Applied
Shan Shan Ng, Zicong Chen, On Ying Yuen, Chau Ming So
Summary: This study presents a new palladium-catalyzed reaction for synthesizing unsymmetrical biaryl compounds containing triflate moiety. The reaction shows high reactivity and chemoselectivity, and can be scaled up without diminishing the yield and selectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Pierre-Louis Lagueux-Tremblay, Celestin Augereau, Pranav Nair, Kwan Ming Tam, Bruce A. Arndtsen
Summary: The use of metal catalysis to form potent acylating agents is an important method to broaden the applicability of carbonylation reactions. However, the reductive elimination of these reactive products has presented a challenge, making the reactions often high temperature and high pressure, and limited in scope. In this study, a mild and versatile palladium catalyzed carbonylative method was developed to generate electrophilic acyl-DMAP salts. The use of triflate anion as a counterion destabilizes Pd(II) and allows for irreversible reductive elimination, while ligand design enables the rapid activation of aryl or vinyl triflates.
Article
Chemistry, Organic
Fusheng Bie, Xuejing Liu, Han Cao, Yijun Shi, Tongliang Zhou, Michal Szostak, Chengwei Liu
Summary: The Pd-catalyzed double-decarbonylative synthesis of aryl thioethers involves an aryl exchange reaction between amides and thioesters, with amides serving as aryl donors and thioesters as sulfide donors. The use of Pd/Xantphos without any additives promotes aryl exchange by C(O)-N/C(O)-S cleavages, allowing for a wide variety of amides and sulfides to be used in the reaction.
