Article
Chemistry, Organic
Tong -Yang Cao, Lin Qi, Wei Dong, Zhi-Min Yan, Shi-Chao Ji, Jian-Long Du, Linlin Zhang, Wei Li, Li-Jing Wang
Summary: In this study, we developed a NIS-promoted selective amino-diazidation and amino-iodoazidation reaction method, which allows the direct synthesis of compounds containing multiple nitrogen moieties in one step. The method is metal-free and offers excellent functional group compatibility and mild reaction conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Tong-Yang Cao, Lin Qi, Wei Dong, Zhi-Min Yan, Shi-Chao Ji, Jian-Long Du, Linlin Zhang, Wei Li, Li-Jing Wang
Summary: In this study, a highly selective NIS-promoted amino-diazidation and amino-iodoazidation of O-homoallyl benzimidates with NaN3 was reported. The method allows for the direct synthesis of a variety of vicinal diazido-substituted 1,3-oxazines and vicinal iodoazido-substituted 1,3-oxazines in a controlled manner.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Zhong-Lin Tao, Scott E. Denmark
Summary: Enantioselective diamination of alkenes is an important method for accessing enantioenriched, vicinal diamines, with broad applications in asymmetric synthesis. Despite lagging behind dihydroxylation of olefins, successful methods using different reaction mechanisms have been developed for enantioselective olefin diamination. This review highlights recent advances and limitations in the field, aiming to inspire further developments.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Eric Cots, Jeroen Rintjema, Fernando Bravo, Kilian Muniz
Summary: A previously unreported meso form of the catalysts was discovered during the upscaling process. A new scalable route was developed to prevent epimerization of the lactamide arms, leading to more effective and time-saving syntheses of the precatalysts. The catalysts obtained from these procedures have been utilized in published reactions, achieving the highest enantiomeric excess ever reported.
Article
Chemistry, Organic
Jie Cao, Daqi Lv, Fei Yu, Mong-Feng Chiou, Yajun Li, Hongli Bao
Summary: The vicinal diamine motif is important in natural products, drug design, and organic synthesis, and developing methods for synthesizing vicinal diamines has long been of interest. This study reports on a regioselective intermolecular three-component vicinal diamination reaction using styrenes, acetonitrile, and azodicarboxylates. The diamination products can be obtained in moderate to excellent yields via the Ritter reaction, and synthetic applications and theoretical studies of this reaction have been conducted.
Article
Chemistry, Multidisciplinary
Yuno Oe, Ryuhei Yoshida, Airi Tanaka, Akiya Adachi, Yuichiro Ishibashi, Takashi Okazoe, Kohsuke Aikawa, Takuya Hashimoto
Summary: This study reports the development of a novel N-fluorinated imide (NFC) as a synthetic handle for the one-step derivatization to amines, sulfonamides, and sulfamides. It also demonstrates the superior reactivity of NFC in copper-catalyzed imidation of benzene derivatives and imidocyanation of aliphatic alkenes, overcoming the limitations of NFSI-mediated reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Xiaoyu Zhang, Yinlei Zhang, Xiaohong Li, Bowen Li, Shiji Xiao, Yongming Tang, Peizhong Xie, Teck-Peng Loh
Summary: This study presents a novel organophotoredox/DABCO catalytic system for the fluoroalkylation of activated allylic acetates via radical-radical coupling. The method offers mild reaction conditions, high selectivity, and broad substrate compatibility, allowing for the incorporation of diverse bioactive molecules, FDA-approved drugs, and amino acid derivatives. This expands the synthetic toolbox for the construction of fluorine-containing molecules.
Article
Chemistry, Organic
Setareh Saryazdi, Sean Parkin, Robert B. Grossman
Summary: We present two new methods for the 1,2-diamination of alkenes. The first method involves the 1,3-dipolar cycloaddition of an azidium ion with an alkene, resulting in the formation of a 1,2,3-triazolinium ion. Alternatively, an intramolecular azide-alkene cycloaddition followed by N-benzylation can also yield the same product. The second method involves the hydrogenation of the 1,2,3-triazolinium ion using Raney Ni, which removes the central N atom and gives the 1,2-diamine product. The stereochemistry of the alkene is generally preserved in the 1,2-diamine, although there may be exceptions.
Review
Chemistry, Organic
Xiang Chen, Fang Xiao, Wei-Min He
Summary: The difunctionalization of carbon-carbon double bonds is a powerful tool in synthetic chemistry to enhance the complexity of molecules by introducing two novel functional groups in one pot. Research on difunctionalization of alkenes involving the participation of a N source is a hotspot due to the broad existence of N-containing functional groups in various compounds, and further developments in this area are expected.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Wen-Jun Han, Jian-Wu Zhang, Chao-Xian Yan, Jia-Wei Wang, Pan-Pan Zhou, Bing Han
Summary: A radical [1,4]-oxygen-atom transfer has been achieved through the reaction of linear alkyne-tethered ketoximes and ethynylbenziodoxolones (EBX) under sequential catalytic conditions. Mechanistic studies reveal a cascade process involving O atom radical cyclization, alkynylation, N-O bond photocleavage, and subsequent N,O-diradical rearrangement. By varying the catalytic sequences, a series of structurally important 3H-pyrrol-3-ones and chlorinated furo[3,2-b]pyrroles were synthesized, accompanied by an O atom shift, using Cu/Ir photosensitization and Cu/Ir photosensitization/AlCl3 catalysis, respectively.
Article
Chemistry, Multidisciplinary
Satoshi Minakata, Hayato Miwa, Kenya Yamamoto, Arata Hirayama, Sota Okumura
Summary: This study demonstrates the stereospecific, substrate-controlled intermolecular anti- and syn-1,2-diaminations of unactivated alkenes using an iodine catalyst. The combined use of the two methods allows access to all diastereomeric forms of 1,2-diamines, even in the presence of E- and Z-alkenes, with the resulting products easily convertible into free vicinal diamines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Peng Wang, Honghai Zhang, Xingliang Nie, Tianxiao Xu, Saihu Liao
Summary: Sulfonyl fluorides have potential applications in chemical biology and drug discovery, but their synthesis is challenging. This study presents a stable fluorosulfonyl radical reagent that enables radical fluorosulfonylation reactions through photoredox catalysis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Xinhan Li, Hengyuan Zhao, Li Meng, Jun Dong, Chunhui Yang, Zixiang Wei, Xianming Wang, Jianbin Xu, Baomin Fan
Summary: This study describes the visible-light photoredox intermolecular catalysis of N-arylacrylamides that are alpha-C-H functionalized with aryl tertiary amines. The photocatalyst serves as a chemical switch to trigger two different reaction pathways, leading to the synthesis of two different products from the same starting material. By adjusting the reaction conditions, oxidative cyclizations or addition products can be selectively synthesized with good to high yields and excellent atom economy.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Fang Zhou, Shaolin Zhu
Summary: Here, a chiral selective nickel-hydride catalyzed hydroalkylation method is reported for the synthesis of structurally diverse beta-chiral amides from readily accessible beta-alkyl-alpha,beta-unsaturated amides. The regio-reversed hydronickellation process provides a complementary approach to access enantioenriched beta-functionalization amides with a stereocenter at the beta-position.
Article
Chemistry, Multidisciplinary
He Huang, Tristan H. Lambert
Summary: A method for the regiodivergent aminooxygenation of aryl olefins under electrophotocatalytic conditions is described, which utilizes a trisaminocyclopropenium ion catalyst and visible light irradiation to convert aryl olefins to oxazoline products with high selectivity. By choosing between water and urethane as reagents, different derivatives of 2-amino-1-ol or 1-amino-2-ol can be synthesized from the same substrate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Zhuang Li, Xian-Yan Cheng, Ning-Yuan Yang, Ji-Jun Chen, Wen-Yue Tang, Jun-Qian Bian, Yong-Feng Cheng, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: A cobalt-catalyzed enantioconvergent radical Negishi C(sp(3))-C(sp(2)) cross-coupling has been developed, providing access to a range of enantioenriched 1,1-diarylmethanes with good yield and moderate enantioselectivities. Key to this discovery is the use of a chiral multidentate anionic N,N,P-ligand to coordinate with the cobalt catalyst and control the chiral environment.
Article
Chemistry, Organic
Xiao-Long Su, Sheng-Peng Jiang, Liu Ye, Guo-Xing Xu, Ji-Jun Chen, Qiang-Shuai Gu, Zhong-Liang Li, Xin-Yuan Liu
Summary: A new copper-catalyzed C(sp(3))-C(sp(2)) cross-coupling reaction has been developed for the synthesis of pharmaceutically useful compounds. The key to success lies in the use of a proline-based ligand to enhance the reducing capability of copper, allowing the conversion of benzyl bromides to radical species under ambient conditions. The reaction shows excellent functional group tolerance and a broad substrate scope.
Article
Chemistry, Multidisciplinary
Yu-Feng Zhang, Xiao-Yang Dong, Jiang-Tao Cheng, Ning-Yuan Yang, Li-Lei Wang, Fu-Li Wang, Cheng Luan, Juan Liu, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: This study demonstrates the successful use of sulfoximines as ammonia surrogates for enantioconvergent radical C-N coupling with diverse racemic secondary alkyl halides, achieving high yields and enantioselectivity. The obtained alpha-chiral primary amines can be converted to various synthetic building blocks, ligands, and drugs, highlighting the potential of enantioconvergent radical cross-coupling as a general chiral carbon-heteroatom formation strategy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Huan Zhou, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: Transition-metal-catalyzed asymmetric C-(sp(3))-C cross-coupling is an efficient method for the rapid synthesis of enantioenriched molecules. Chiral copper catalysts have been designed to promote a variety of asymmetric radical C(sp(3))-C cross-coupling reactions with high efficiency and enantioselectivity. The key to success lies in the design of chiral ligands to initiate the reaction and achieve enantiocontrol over the highly reactive prochiral alkyl radical species.
Article
Chemistry, Organic
Na Wang, Li-Wen Fan, Jin Zhang, Qiang-Shuai Gu, Jin-Shun Lin, Guo-Qiang Chen, Xin-Yuan Liu, Peiyuan Yu
Summary: This study investigates the highly enantioselective intramolecular hydroamination reaction and uncovers its uncommon reaction mechanism. The reactivity of this reaction is primarily determined by the substituents on the internal carbon of the alkene, as well as the substituents on the terminal alkene carbons. The lower acidity of chiral phosphoric acids compared to chiral NTPAs results in a slower reaction.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Wu Yang, Lin Liu, Jiandong Guo, Shou-Guo Wang, Jia-Yong Zhang, Li-Wen Fan, Yu Tian, Li-Lei Wang, Cheng Luan, Zhong-Liang Li, Chuan He, Xiaotai Wang, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: In this study, a strategy for catalytic enantioselective hydroxylation of prochiral dihydrosilanes is described. The reaction provides Si-chiral silanols with high enantioselectivity and excellent functional group compatibility. Furthermore, the obtained products exhibit high structural diversity and can be further transformed using established synthetic schemes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peng-Fei Wang, Jiao Yu, Kai-Xin Guo, Sheng-Peng Jiang, Ji-Jun Chen, Qiang-Shuai Gu, Ji-Ren Liu, Xin Hong, Zhong-Liang Li, Xin-Yuan Liu
Summary: In this study, a copper/chiral N,N,N-ligand catalytic system was developed for the enantioconvergent cross-coupling of benzyl/propargyl halides with alkenylboronate esters, providing enantiocontrol over highly reactive alkyl radicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Fu-Li Wang, Chang-Jiang Yang, Ji-Ren Liu, Ning-Yuan Yang, Xiao-Yang Dong, Ruo-Qi Jiang, Xiao-Yong Chang, Zhong-Liang Li, Guo-Xiong Xu, Dai-Lei Yuan, Yu-Shuai Zhang, Qiang-Shuai Gu, Xin Hong, Xin-Yuan Liu
Summary: In contrast to the well-established enantioconvergent radical C(sp(3))-C cross-coupling, the coupling of tertiary electrophiles to forge all-carbon quaternary stereocentres remains unexplored. Here, we demonstrate a general copper-catalysed enantioconvergent C(sp(3))-C(sp) cross-coupling using rational design of chiral ligands. This protocol provides a practical platform for the construction of chiral carbon building blocks of interest in organic synthesis.
Article
Chemistry, Organic
Jun-Bin Tang, Jun-Qian Bian, Yu-Shuai Zhang, Yong-Feng Cheng, Han-Tao Wen, Zhang-Long Yu, Zhong-Liang Li, Qiang-Shuai Gu, Guo-Qiang Chen, Xin-Yuan Liu
Summary: A copper-catalyzed highly anti-selective radical 1,2-alkylarylation of terminal alkynes has been established, providing facile access to various stereo-defined trisubstituted alkenes in high yield under mild reaction conditions.
Article
Chemistry, Multidisciplinary
Xiao-Yang Dong, Zhong-Liang Li, Qiang-Shuai Gu, Xin-Yuan Liu
Summary: This article mainly introduces the research progress on enantioconvergent radical cross-coupling reactions. Compared with chiral nickel catalysts, the study of copper-catalyzed enantioconvergent radical cross-coupling is less explored, primarily due to the weak reducing capability of copper. In recent years, researchers have been dedicated to developing chiral ligands for copper-catalyzed enantioconvergent radical cross-coupling to address the issues of enantiocontrol and reaction initiation speed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xian-Yan Cheng, Yu-Feng Zhang, Jia-Huan Wang, Qiang-Shuai Gu, Zhong-Liang Li, Xin-Yuan Liu
Summary: This paper presents a copper-catalyzed enantioselective intermolecular radical 1,2-carboamination reaction using readily accessible alkyl halides and alkenes. The success of this method is attributed to the conceptual design of a counterion/highly sterically demanded ligand coeffect, which promotes the ligand exchange and formation of chiral C-N bonds. The reaction is versatile and delivers various chiral amine building blocks of interest in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Ji-Jun Chen, Jia-Heng Fang, Xuan-Yi Du, Jia-Yong Zhang, Jun-Qian Bian, Fu-Li Wang, Cheng Luan, Wei-Long Liu, Ji-Ren Liu, Xiao-Yang Dong, Zhong-Liang Li, Qiang-Shuai Gu, Zhe Dong, Xin-Yuan Liu
Summary: Unnatural chiral amines are in high demand in the pharmaceutical and agrochemical industries. This study presents a copper-catalysed method using chiral tridentate anionic ligands for highly selective N-alkylation of aliphatic amines. The method allows for the direct conversion of feedstock chemicals into unnatural chiral α-amino amides under mild conditions, demonstrating excellent enantioselectivity and functional group tolerance. The use of multidentate anionic ligands overcomes the issue of transition metal catalyst poisoning.