Article
Chemistry, Multidisciplinary
Wei-Yuan Ma, Guan-Yu Han, Shaolin Kang, Xiaobo Pang, Xue-Yuan Liu, Xing-Zhong Shu
Summary: The study presents a new method for synthesizing enantioenriched 1,4-dienes using cobalt catalysis, demonstrating high enantiospecificity and chemoselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Lei Su, Guobin Ma, Yanhong Song, Hegui Gong
Summary: This study demonstrates a facile method for constructing C-3a vinyl substituted hexahydropyrrolidinoindolines based on Ni-catalyzed reductive coupling, showcasing remarkable compatibility with a wide range of alkyl-decorated vinyl triflates, including sterically hindered branched vinyl groups.
Article
Chemistry, Organic
Tingzhi Lin, Pengcheng Qian, Yan-En Wang, Mingjie Ou, Ning Cui, Yu Ye, Rui Hua, Dan Xiong, Fei Xue, Patrick J. Walsh, Jianyou Mao
Summary: A direct and convenient method for the synthesis of aryl/alkenyl alkyl ketones has been developed. This method overcomes the limitations of previous methods and avoids the use of organometallic reagents.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xuejing Peng, Jingxian Huang, Guan-Yu Han, Xing-Zhong Shu
Summary: In this manuscript, a dynamic kinetic cross-electrophile coupling reaction of benzylic alcohols with alkenyl triflates is reported. This method allows for the replacement of the alcohol group with an alkenyl functionality, resulting in versatile benzyl-substituted cyclic alkenes. The reaction is orthogonal to existing reductive coupling methodologies and tolerates various functional groups.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jens Lindman, Anubha Yadav, Johan Gising, Mats Larhed
Summary: This paper reports a palladium(0)-catalyzed aminocarbonylation reaction using molybdenum hexacarbonyl as a carbon monoxide precursor for the synthesis of N-capped amino acids using aryl and heteroaryl bromides and triflates. The carbon monoxide is generated ex situ and utilized in the palladium-catalyzed reaction chamber. By utilizing this method, 21 N-capped amino acids were synthesized using two series of aryl bromides and aryl triflates with isolated yields between 40% and 91%.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
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
Xiaowei Li, Yuxiu Li, Wenlong Shan, Zemin Wang, Ruihua Liu, Zhong Zhang, Xiangqian Li, Dayong Shi
Summary: Here we report the development of a Ni-catalyzed defluorinative cross-electrophile coupling of gem-difluoroalkenes with alkenyl electrophiles, enabling the formation of C(sp(2))-C(sp(2)) bonds. The reaction exhibits broad functional group compatibility and excellent stereoselectivity, providing access to various monofluoro 1,3-dienes. Additionally, we demonstrate the synthetic transformations and applications of this reaction for the modification of complex compounds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Raymond F. Turro, Julie L. H. Wahlman, Z. Jaron Tong, Xiahe Chen, Miao Yang, Emily P. Chen, Xin Hong, Ryan G. Hadt, K. N. Houk, Yun-Fang Yang, Sarah E. Reisman
Summary: Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation of N-hydroxyphthalimide (NHP) esters and benzylic chlorides were conducted. The study revealed divergent mechanisms for these related transformations, with the mechanism of C(sp(3)) activation changing depending on the reactants used. Kinetic experiments showed that the rate of NHP ester reduction can be tuned by changing the Lewis acid. Spectroscopic studies and DFT calculations provided insights into the catalyst resting state and the origin of enantioinduction for the Ni-BOX catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yan Xu, Tong Su, Jie-Rui Zhang, Hua-Jiao Ding, Yuanji Gao, Minghui Xu, Peng Cao, Ping Hu, Bi-Qin Wang, Bin Chen
Summary: A regio- and stereoselective nickel-catalyzed reductive three-component cross-coupling reaction between 1,3-butadiene, aldehydes, and alkenyl triflates or bromides was developed. This method provides a convenient access to the synthesis of skipped diene compounds bearing various functional groups and heterocyclic moieties. The utility of this reaction was demonstrated by scale-up preparation and diverse transformations.
Article
Chemistry, Organic
Xiaopeng Wu, Jinhang Li, Siyu Xia, Chengjian Zhu, Jin Xie
Summary: We report a thioacylation transfer reaction based on nickel-catalyzed C-C bond cleavage of thioesters with sp(2) hybridized electrophiles. Aryl bromides, iodides, and alkenyl triflates can participate in the thioester transfer reaction, leading to a wide range of structurally diverse new thioesters in yields of up to 98% under mild reaction conditions.
JOURNAL OF ORGANIC CHEMISTRY
(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 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, Organic
Pan Gao, Qingzheng Zhang, Feng Chen
Summary: A new protocol for vinyl sulfide synthesis has been developed using an alkoxy base without the need for metal catalysts. This method allows for the conversion of aryl and alkenyl sulfonium triflates with various functionalities into vinyl sulfides with excellent reactivity. The reaction conditions are mild and safe, without the use of catalysts, transition metals, high-pressure gases, or high temperatures, while still maintaining efficiency.
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
Qi-Chao Shan, Shuai Liu, Yuncheng Shen, Mingming Ma, Xin-Hua Duan, Pin Gao, Li-Na Guo
Summary: This study presents the switchable process of in situ SO2 capture and CF3 migration using peroxyl compounds under iron catalysis. By controlling the structure of peroxides, a variety of keto-functionalized dialkyl sulfones and β-trifluoromethyl ketones were selectively synthesized in good yields under mild conditions.
Article
Chemistry, Organic
Zhen Wang, Yuanyuan Hu, Hongwei Jin, Yunkui Liu, Bingwei Zhou
Summary: In this study, a nickel-catalyzed arylation and alkenylation of tert-cyclobutanols with aryl/alkenyl triflates via a C-C bond cleavage was developed, yielding a variety of α-substituted ketones in moderate-to-good yields. The reaction features earth-abundant nickel catalysis, broad substrate scope, and simple reaction conditions. Preliminary mechanistic experiments suggest involvement of beta-carbon elimination pathways in the catalytic cycle.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
