Article
Chemistry, Multidisciplinary
Zheng Sun, Shuwei Zhang, Qiyuan Ma, Yuemei Li, Han Ding, Yu Yuan, Xiaodong Jia
Summary: A series of furoxan derivatives with N-nitroso groups were efficiently synthesized by TBN-initiated radical sp(3) C-N bond cleavage of 1-nitromethyl-N-aryltetrahydroisoquinolines. This reaction introduces the biologically important furoxan skeleton and N-nitroso group into one molecule, significantly enhancing molecular complexity through a one-step transformation. Mechanistic studies reveal that this reaction is mediated by the in situ generated alpha-carbonyl nitrile oxide, which is formed via TBN-promoted C-N bond cleavage.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yuanyuan Ping, Xiao Li, Qi Pan, Wangqing Kong
Summary: Ligand-directed divergent synthesis is a strategy that can transform common starting materials into distinct molecular scaffolds. This strategy enables the rapid construction of structurally rich collection of small molecules for biological evaluation and reveals novel modes of catalytic transformation, representing one of the most sought-after challenges in synthetic chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ryoma Shimazumi, Riku Tanimoto, Takuya Kodama, Mamoru Tobisu
Summary: This study reports a new UFC reaction that involves the palladium-catalyzed elimination of an isocyanate fragment from an amide, resulting in the formation of carbon-carbon and carbon-heteroatom bonds. This reaction enables the late-stage transformation of the amide functionality.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Demao Chen, Liyun Zhou, Yunyun Liu, Jie-Ping Wan
Summary: The direct three-component reactions of enaminones, aryl hydrazine hydrochlorides, and internal alkynes via Rh(iii) catalysis have enabled the synthesis of N-naphthyl pyrazoles. The use of simple substrates in these synthetic reactions results in the simultaneous construction of dual cyclic moieties, including a pyrazole ring and a phenyl ring, through the sequential formation of two C-N and three C-C bonds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Xiao-Di Su, Zhu-Sheng Yang, Wei Gong, Zhi-Xiang Wang, Xiang-Yu Chen
Summary: We have discovered that N-heterocyclic nitreniums (NHNs) can act as efficient catalysts for charge transfer complex without the need for any additives. The NHN cation acts as an electron acceptor, while the counter-ion I- serves as an electron donor, enabling the synthesis of diverse trisubstituted alkenes and heterocycles.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Leiyang Bai, Yinhao Ma, Xuefeng Jiang
Summary: Through a one-step catalytic operation, this study successfully designed a synthetic pathway for the total synthesis of isocalycanthine and its derivatives, which possess novel structures and alkaloid activities in dimeric cyclotryptamine alkaloids.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Yusuke Ano, Masaya Higashino, Yuki Yamada, Naoto Chatani
Summary: The Pd-catalyzed transformation of N-phthaloyl hydrazones into nitriles involving the cleavage of an N-N bond is reported. The use of N-heterocyclic carbene as a ligand is crucial for the success of the reaction. N-Phthaloyl hydrazones prepared from aromatic aldehydes or cyclobutanones can be applied to this transformation, yielding aryl or alkenyl nitriles, respectively.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Muhammad Aliyu Idris, Kwang Ho Song, Sunwoo Lee
Summary: This study presents a new method for synthesizing acyl fluorides under environmentally friendly conditions without the need for transition-metal catalysts or additives. The methodology demonstrates good functional group tolerance towards various groups.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Yujin Jang, Weixia Deng, Ivan S. S. Sprague, Vincent N. G. Lindsay
Summary: An expedient approach for the synthesis of challenging β-fluoroamides from readily accessible cyclopropanone equivalents is reported. Following the addition of pyrazole used here as a transient leaving group, silver-catalyzed regiospecific ring-opening fluorination of the resulting hemiaminal leads to a β-fluorinated N-acylpyrazole intermediate reactive to substitution with amines, ultimately affording β-fluoroamides. The process could also be extended to the synthesis of β-fluoroesters and γ-fluoroalcohols via the addition of alcohols or hydrides as terminal nucleophiles, respectively.
Article
Chemistry, Organic
Tzu-Lun Liu, Meng-Li Jhou, Cheng-En Hsieh, Chia-Jung Lin, Hsiu-Hui Su, Chih-Ming Chou
Summary: This study presents a protocol for the preparation of functionalized N-allyl-N-aryl sulfonamides via palladium-catalyzed intramolecular decarboxylative N-allylation reaction, showing good regioselectivity. Additionally, transformation of N-allyl-N-aryl sulfonamide into 4-aryl-1,2,3,4-tetrahydroquinoline and nitrogen-containing beta-hydroxysulfide bioactives has been demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Xiaoyun Pu, Yaqi Zhang, Xiaobo He, Xinhuan Zhang, Long Jiang, Rihui Cao, Man Kin Tse, Liqin Qiu
Summary: A highly efficient method for the asymmetric synthesis of N-substituted 4-quinolones through C-N coupling reaction was developed using palladium catalysis. Various chiral quinolones with high enantioselectivity (up to 95% ee) and excellent yield (up to 99%) were easily obtained using palladium acetate and chiral ferrocene bisphosphine as auxiliary ligand. Racemic derivatives could also be synthesized using a transition metal-free strategy with potassium hydroxide in DMSO. The influence of temperature on the configurational stability of these C-N axially chiral compounds was also investigated. The efficient functionalization at 3-position further expands the application range of this synthetic technique.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Xu Zhang, Zhen-Yu Wang, Xing Wang, Hui Xu, Hui-Xiong Dai
Summary: In this study, the synthesis of functionalized styrenes via palladium-catalyzed Suzuki-Miyaura cross-coupling reaction between aryl ketone derivatives and potassium vinyltrifluoroborate was reported. The use of pyridine-oxazoline ligand was essential for the cleavage of unstrained C-C bond. Various functional groups and biologically important molecules were well tolerated. The orthogonal Suzuki-Miyaura coupling demonstrated its synthetic practicability.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Hui Chen, Ranran Cui, Yahui Zhang, Yu Gao, Haijun Chen
Summary: In this study, a mild and metal-free synthesis of 3,3'-bisindoles is reported. The synthesis involves removal of the Fmoc group and subsequent cleavage of C-C and C-N bonds to generate the desired product. The resulting scaffold is suitable for further functionalization and exhibits interesting photophysical properties in both solution and solid state, suggesting its potential application in organic luminophores.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Yongliang Tu, Junfeng Zhao
Summary: Arylhydrazines and quaternary ammonium salts have shown versatile reactivity in Pd-catalyzed coupling reactions, acting as aryl or alkyl donors. Various coupling reactions involving different reaction partners and mechanistic elucidations have been summarized, providing important insights for future research.
Article
Chemistry, Physical
Licheng Wu, Tong Wang, Chenyang Gao, Wenyi Huang, Jingping Qu, Yifeng Chen
Summary: In this study, a new Pd-catalyzed strategy was reported for the construction of azepines through C-N bond cleavage reactions, showing good functional group tolerance and 100% atom economy. The use of 3-alkylidenepyrrolidine as a precursor for zwitterionic salts and the in situ formation of an allyl-palladium intermediate were key factors for the successful cascade [5 + 2] cycloaddition.
