Article
Chemistry, Multidisciplinary
Dong Liu, Zhao-Ran Liu, Cong Ma, Ke-Jin Jiao, Bing Sun, Lei Wei, Julien Lefranc, Simon Herbert, Tian-Sheng Mei
Summary: A novel strategy using nickel catalysis and electrochemistry has been developed for the construction of sulfoximine derivatives, achieving excellent functional group tolerance and yield under mild reaction conditions. Preliminary mechanistic studies suggest that anodic oxidation of a Ni-II species is crucial for promoting the reductive elimination of a C-N bond from a resulting Ni-III species at room temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Yang -yang Li, Bing Gao
Summary: N-functionalization of free sulfoximines is a significant method for modifying their properties for various applications. This study presents a rhodium-catalyzed N-allylation of free sulfoximines (=NH) with allenes, enabling chemo- and enantioselective ?-hydroamination of allenes and gem-difluoroallenes. The synthesis of sulfoximine products using this method is also demonstrated.
Article
Chemistry, Organic
Hongsheng Nie, Zhicheng Xiong, Meiqian Hu, Shuai Zhang, Changsheng Qin, Shoucai Wang, Fanghua Ji, Guangbin Jiang
Summary: An efficient and practical method for the synthesis of N-sulfonyl sulfoximines was developed using aryldiazonium tetrafluoroborates and DABSO as SO2 insertion reagents with NH-sulfoximines under mildly basic conditions. This method offers easy operation, readily available substrates, and mild reaction conditions. A tentative mechanism, involving aryldiazonium tetrafluoroborates as radical donors and the trapping of aryl radicals by SO2 to generate arylsulfonyl radicals, is proposed.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Florian Papp, Daniel Sowa Prendes, Sourav Manna, Ann-Katrin Seitz, Sofiya Kostiukovska, Julian Loeffler, Viktoria H. Gessner, Lukas J. Goossen
Summary: Palladium complexes with ylide-functionalized phosphine ligands catalyze the arylation of N-protected hydantoins with aryl chlorides, enabling the synthesis of a wide variety of hydantoins, including derivatives of the anticonvulsant drugs phenytoin and mephenytoin. Selective monoarylations, sequential diarylations, and arylation-alkylation sequences have been achieved, along with stepwise deprotection strategies.
Article
Chemistry, Organic
Min Zhang, Zhangyi Fu, Anping Luo, Xingwen Pu, Menglei Wang, Ying Huang, Yudong Yang, Jingsong You
Summary: The study presents a concise route for site-selective arylation of polycyclic aromatic hydrocarbons with easily available aryl sources, contributing to the bottom-up preparation of pi-extended PAHs. Additionally, a C8-H annulation protocol has been developed to rapidly assemble benzanthrones by simply switching the solvent to 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP).
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Ding Ma, Chenyang Wang, Deshen Kong, Yongliang Tu, Peng Shi, Carsten Bolm
Summary: Palladium-catalyzed carbonylation reactions with Cr(CO)(6) as carbonyl source are key for the preparation of N-ynonylsulfoximines from NH-sulfoximines and bromoalkynes, affording the corresponding products in good yields at room temperature with a wide range of substrate combinations.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Pan Qiu, Xuelun Duan, Ming Li, Yubin Zheng, Wangze Song
Summary: A metal-, base-, and additive-free N-acylation of sulfoximines was developed using an organic photoredox catalyst under mild conditions. This green strategy showed broad substrate scope, good compatibility with air, and high yields.
Article
Chemistry, Organic
Mingpan Yan, Longzhi Zhu, Xingxing Zhang, Shuang-Feng Yin, Nobuaki Kambe, Renhua Qiu
Summary: An efficient methodology for the synthesis of large sterically hindered triarylamines in a single step was developed, with good to excellent yields using inexpensive nickel catalyst. Various bromides and substituted 8-aminoquinolines can be tolerated in the reaction, and preliminary fluorescence results indicate potential in material chemistry for these sterically hindered and conjugated triarylamines.
Article
Chemistry, Organic
Sonbidya Banerjee, Manmath Mishra, Tharmalingam Punniyamurthy
Summary: In this study, the Cu-catalyzed cross-dehydrogenative coupling of the C7 C-H bond of indolines with sulfoximines has been successfully achieved. The reaction can also be extended to the cross-dehydrogenative coupling of N-aryl 7-azaindoles with monoselectivity. The use of first-row copper catalysis, substrate scope, and late-stage synthetic applications are important practical features of this study.
Article
Chemistry, Multidisciplinary
Daniel Sowa Prendes, Florian Papp, Nagesh Sankaran, Nardana Sivendran, Frederike Beyer, Christian Merten, Lukas J. Goossen
Summary: Arylglycines, which are important pharmacophores in several top-selling drugs, can now be synthesized from abundant aryl chlorides using a Pd-catalyzed Schollkopf-type amino acid synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Chao Liu, Liangliang Song, Luc Van Meervelt, Erik V. Van der Eycken
Summary: An excellent chemo- and regioselective palladium-catalyzed cascade intermolecular N-arylation/aryl-aryl coupling process has been developed, resulting in the synthesis of diverse C4-substituted phenanthridinones. The method shows broad substrate scope and excellent functional group tolerance, allowing for further derivatization to prepare multiple-substituted phenanthridinones in moderate to high yields.
MOLECULAR CATALYSIS
(2021)
Article
Chemistry, Applied
Bingxiang Xue, Jie Shen, Sourav Manna, Angelino Doppiu, Lukas J. Goossen
Summary: A new catalyst has been discovered that can selectively introduce a primary amino group into aromatic compounds, and it can efficiently promote the amination reaction to synthesize primary anilines within 30 minutes.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Sushma Naharwal, Narendra Dinkar Kharat, Chikkagundagal K. Mahesha, Kiran Bajaj, Rajeev Sakhuja
Summary: Regioselective C-arylation and C,N-diarylation of 2-aryl-2,3-dihydrophthalazine-1,4-diones have been achieved successfully using diaryliodonium salts under base-mediated slightly modified Pd catalyzed conditions. These ligand-driven transformations afforded a wide range of diversely decorated bi(hetero)aryls in good-to-excellent yields, while N-arylated product can be obtained under similar Pd-catalyzed conditions in the absence of a ligand.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Cunbo Wei, Lizhu Zhang, Zhonghua Xia
Summary: A gold-catalyzed Heck reaction was developed for the synthesis of stilbenes and bistyryl complexes by cross-coupling aryl and styryl iodides with styrenes. The reaction exhibited good functional-group tolerance and mild conditions, assisted by a hemilabile P,N ligand. The mechanism may involve migratory insertion and beta-hydride elimination steps.
Article
Multidisciplinary Sciences
Yu Chang, Chuandong Xie, Hong Liu, Shengli Huang, Pengfei Wang, Wenling Qin, Hailong Yan
Summary: 1,2-Azoles are privileged structures in many natural products and drugs. The authors report an atroposelective synthesis of two types of axially chiral 1,2-azoles through vinylidene ortho-quinone methide intermediates.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Shan Shan Ng, Zicong Chen, On Ying Yuen, Chau Ming So
Summary: A novel family of phosphine ligands was designed and synthesized, which showed excellent catalytic efficiency in the synthesis of triortho-substituted biaryls. The coordination mode of the ligand with palladium was confirmed by single-crystal X-ray crystallography.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Miao Wang, Chau Ming So
Summary: A newly developed phosphine ligand with a C2-cyclohexyl group on the indole ring was successfully applied in a chemoselective Sonogashira coupling reaction, achieving an inversion of the conventional chemoselectivity order. This study also provided an efficient approach to the synthesis of polycyclic aromatic hydrocarbons (PAHs) and the natural product analogue.
Article
Chemistry, Inorganic & Nuclear
Ka Yee Yee, Man Pan Leung, Man Ho Tse, Pui Ying Choy, Fuk Yee Kwong
Summary: This paper presents the first general examples of palladium-catalyzed direct C-H olefination of polyfluoroarenes using alkenyl tosylates as electrophilic coupling partners. Good-to-excellent yields of olefinated polyfluoroarenes can be obtained by employing the Pd/L1 catalyst system. The reaction exhibits good structural and functional compatibility, and particularly smooth reactivity for steric demanding and heterocyclic alkenyl tosylates. It can be practically performed on a gram-scale without significant loss of product yields.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kin Boon Gan, Rong-Lin Zhong, Zhen-Wei Zhang, Fuk Yee Kwong
Summary: In this study, a rational design of a new collection of chiral phosphines featuring a C-N axial chirality is presented. These phosphines were successfully applied in the enantioselective synthesis of highly steric hindered tetra-ortho-substituted biaryls. It was found that the carbazolyl framework played a crucial role in facilitating the reaction through a fleeting Pd-N/Pd-pi coordination.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Tianyi Liu, Kin Boon Gan, Rong-Lin Zhong, Xinwei He, Fuk Yee Kwong
Summary: This study reports a redox-neutral benzylic C-O cyclization under transition-metal-free conditions utilizing the Tf anion as the leaving group. The protocol delivers a series of captivating helical compounds with various functionality in good-to-excellent yields. It is particularly notable that sterically hindered helical compounds are conformationally stable. In addition, bihelical multiple-ring systems potentially useful in material chemistry can also be easily obtained using this method.
Review
Chemistry, Multidisciplinary
Man Ho Tse, Pui Ying Choy, Fuk Yee Kwong
Summary: This article presents a promising collection of phosphine ligands and explores their applications in modern arylation processes. Using a readily accessible 2-arylindole scaffold, three major phosphino-moiety-positioned ligand series can be generated. The study shows that the balance of steric and electronic properties of phosphine ligands is crucial for the success of the reaction.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Review
Chemistry, Multidisciplinary
Pui Ying Choy, Kin Boon Gan, Fuk Yee Kwong
Summary: Sonogashira cross-coupling protocol allows the construction of C(sp(2))-C(sp) bond through the reaction between aryl/vinyl halide and terminal alkyne. The resulting internal alkynes are versatile for the synthesis of various functionalized alkyne-containing scaffolds or as valuable synthetic synthons. The reaction conditions can be adjusted to activate hindered and/or electron-rich electrophiles, and Pd-catalyzed copper-free Sonogashira coupling reaction has gained attention for being more environmentally friendly and allowing convergent synthesis in a one-pot manner.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Miao Wang, On Ying Yuen, Chau Ming So
Summary: This paper presents the first examples of palladium-catalyzed desulfinative cross-coupling reaction of polyhalogenated aryl triflates with aryl sulfinate salts. The catalyst system exhibited excellent reactivity and chemoselectivity in this reaction, which had a wide substrate scope and provided a simple method for constructing functionalized biaryl motifs. The interaction between the indolyl phosphine ligand and the Pd center played a key role in the reactivity and chemoselectivity of this reaction.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Liangbin Yu, Junjun Liu, Shiyu Xiang, Taotao Lu, Ping Ma, Qingyang Zhao
Summary: By using a chiral silver phosphate catalyst, a direct 5-endo-dig nucleophilic cyclization of 2-alkynylanilins was achieved under mild conditions, leading to the synthesis of various C-C axially chiral 2arylindoles with high yields and enantioselectivities. Control experiments showed the cooperative catalysis of AgOAc and chiral phosphoric acid, with the former accelerating the desired transformation and the latter improving enantioselectivity. Additionally, the synthetic applications and thermal stability of the products were investigated, making it the first example of silver-catalyzed enantioselective de novo synthesis of C-C axially chiral indole skeletons.
Article
Multidisciplinary Sciences
Qingyang Zhao, Le Yu, Yao-Du Zhang, Yong-Qiang Guo, Ming Chen, Zhi-Hui Ren, Zheng-Hui Guan
Summary: In this study, a selective C(alkyl)-C(vinyl) bond cleavage strategy was achieved through a transient directing group mediated retro-Diels-Alder reaction. This unprecedented strategy exhibits good tolerances and offers new opportunities for late-stage modifications of complex molecules.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Pui Ying Choy, Man Ho Tse, Fuk Yee Kwong
Summary: Transition metal-catalyzed borylation is a powerful strategy for synthesizing organoboron compounds, and it finds widespread applications in various fields. This review provides a concise summary of recent advances in palladium- and rhodium-catalyzed borylation, highlighting catalyst systems, substrates scope, and reaction conditions. The discussion also includes the diverse array of borylative products obtained and future directions for more efficient and selective methodologies.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Shiyu Xiang, Taotao Lu, Junjun Liu, Qingyang Zhao
Summary: An unprecedented redox transformation of β-sulfinyl esters to generate sulfinate anions has been discovered, enabling the asymmetric sulfonylation of vinylidene o-quinone methides and providing various sulfone-based axially chiral styrenes with excellent enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Qingjing Yang, Jian Zhou, Jun (Joelle) Wang
Summary: An enantioselective hydrophosphination reaction of alkenyl isoquinolines is achieved using a copper-chiral diphosphine ligand catalyst. This method provides a straightforward and efficient synthesis of chiral phosphines containing an isoquinoline moiety, with high yields and excellent enantioselectivities. Additionally, these chiral phosphine products can serve as useful bidentate P,N-ligands with potential applications in asymmetric catalysis.
Article
Chemistry, Organic
Yanan Liu, Pui Ying Choy, Demao Wang, Mengdi Wu, Qiang Tang, Xinwei He, Yongjia Shang, Fuk Yee Kwong
Summary: A 1,8-diazabicyclo[5.4.0]-undec-7-ene-promoted cascade double-annulation of ortho-alkynyl quinone methide is developed for constructing of 2-aryl-4-hydroxybenzo-[c]-chromen-6-ones. This method offers operational simplicity and good functional group compatibility.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zicong Chen, Changxue Gu, On Ying Yuen, Chau Ming So
Summary: This study described a selective palladium-catalyzed direct α-arylation reaction using chloroaryl triflates and carbonyl compounds. The reaction exhibited excellent chemoselectivity towards the Ar-Cl bond with a broad substrate scope and high product yields. The electronic and steric effects of the -PR2 group and C2-alkyl group were found to be crucial for the reactivity and selectivity of the α-arylation reaction. This chemodivergent approach was also successfully applied in the synthesis of flurbiprofen and its derivatives (-OMe and -F).
