Article
Chemistry, Physical
Zhiqian Yu, Qianhui Liu, Yudong Yang, Jingsong You
Summary: This study demonstrates that phenolic compounds can serve as effective ligands to control the regioselectivity of ortho-C-H arylation reactions, enabling the synthesis of various biaryl phosphines in a streamlined and practical manner. The phosphine ligand library shows great potential in catalytic coupling reactions and exhibits unique chemoselectivity when compared with commercially available classic phosphine ligands.
Article
Chemistry, Physical
Man Ho Tse, Rong-Lin Zhong, Fuk Yee Kwong
Summary: In this study, a general Pd-catalyzed Miyaura borylation of sterically hindered aryl chlorides was achieved using a tailor-made phosphine ligand. The success of this reaction demonstrated the possibility of coupling highly sterically congested electrophilic partners and showed good functional group compatibility. The ligand-enabled C-B bond formation could provide fundamental knowledge for developing catalyst systems suitable for other highly sterically hindered cross-coupling reactions.
Article
Chemistry, Applied
Masahiro Sai
Summary: The tetraarylpyrrole-based phosphine ligand L1 in combination with Pd(dba)(2) serves as an effective catalyst for the Buchwald-Hartwig amination reaction, allowing rapid coupling of a variety of amines with aryl chlorides and selective monoarylation of aliphatic primary amines under specific conditions. Comparison experiments demonstrate the superior catalytic activity of L1 in the Pd-catalyzed C-N coupling of various amines.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Jinhui Cai, Li-Gang Bai, Yiliang Zhang, Zhen-Kai Wang, Fei Yao, Jin-Huang Peng, Wei Yan, Yan Wang, Chao Zheng, Wen-Bo Liu
Summary: This study presents an efficient strategy for assembling enantioenriched pyridine derivatives by forming three bonds and one quaternary stereocenter simultaneously in a single reaction step. The reaction utilizes bio-renewable 2-MeTHF as the solvent, features mild reaction conditions, and shows good functional group compatibilities and enantioselectivities.
Article
Chemistry, Applied
Joshua W. M. MacMillan, Travis Lundrigan, Giulio Volpin, Sherif J. Kaldas, Philipp M. Holstein, Mark James Ford, Nicolas Guimond, Mark Stradiotto
Summary: The mono- and alpha-arylation of 2-tetrahydropyranyl O-protection of hydroxyacetone is achieved using a catalyst system consisting of [Pd(cinnamyl)Cl](2) and the JosiPhos ligands PhPF-tBu or (4-CF3Ph)PF-tBu. The transformation is successful with ortho-substituted aryl bromides and triflates, even in the presence of potentially contending functionalities including chloro groups.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
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, 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, Multidisciplinary
Akihisa Matsuura, Yusuke Ano, Naoto Chatani
Summary: In this study, nucleophilic aromatic substitution reactions of non-activated aryl fluorides with amide enolates were reported. The reaction conditions were relatively mild, and lactams also participated in the reaction. DFT calculations suggested that the reaction proceeded through a concerted SNAr pathway.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Filip Horky, Ivana Cisarova, Petr Stepnicka
Summary: This study described the synthesis of new donor-unsymmetric dppf congeners and their conversion into air-stable Pd(0) complexes, which showed high catalytic activity and selectivity in the Pd-catalyzed C-H arylation reaction. The complex [Pd(ma)(2)] performed the best in synthesizing 2-arylbenzoxazoles with high yield and selectivity under environmentally friendly conditions.
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, Multidisciplinary
Chuanyong Wang, Xiaobo Hu, Cheng Xu, Qiangqiang Ge, Qingliang Yang, Jianqi Xiong, Wei-Liang Duan
Summary: A novel nickel-catalyzed enantioselective C(sp(2))-P cross-coupling has been developed for the synthesis of P-stereogenic phosphine oxides. The reaction of racemic secondary phosphine oxides with alkenyl/aryl bromides produces P-stereogenic phosphine oxides with high yields and enantioselectivities. The method shows excellent tolerance towards various functional groups and has been applied for late-stage functionalization and product transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Mei-Ling Wang, Hui Xu, Han-Yuan Li, Biao Ma, Zhen-Yu Wang, Xing Wang, Hui-Xiong Dai
Summary: The Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is achieved via palladium-catalyzed ligand-promoted C-C bond cleavage, providing good to excellent yields of the alkene product. Further applications in the late-stage olefination of drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol. By using ketone as both the directing group and the leaving group, 1,2-bifunctionalization is achieved through sequential ortho-C-H alkylation/ipso-Heck olefination.
Article
Chemistry, Organic
Fan Luo, Hui Zhou, Xiao-Bei Chen, Xue-Jun Liu, Xiao-Dong Chen, Peng-Fei Qian, Xin-Ping Wu, Wei Wang, Shi-Lei Zhang
Summary: A simple and efficient protocol for preparing challenging alpha-aryl primary amides has been developed. This metal-free coupling process involves the electrophilic activation of alpha-silyl nitrile and rearrangement with aryl sulfoxide.
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, Multidisciplinary
Xiaomin Shu, De Zhong, Yanmei Lin, Xiao Qin, Haohua Huo
Summary: We report a general and modular approach for the direct enantioselective alpha-arylation of saturated azacycles and acyclic N-alkyl benzamides via nickel/photoredox dual catalysis. This method requires no oxidants or organometallic reagents, features broad substrate scope and high enantioselectivities, and is applicable to late-stage diversification of medicinally relevant complex molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Zicong Chen, Chau Ming So
Article
Chemistry, Multidisciplinary
On Ying Yuen, Chau Ming So
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Organic
Zicong Chen, Chau Ming So
Summary: Palladium-catalyzed cross-coupling reactions are essential for C-C bond formation, with new catalyst development driving progress in the field. A new easily accessible phenylpyrazole phosphine ligand was developed in this study, leading to an efficient catalyst for cross-coupling reactions. This method offers a practical alternative for synthesizing multi-substituted alkenes under mild conditions.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Shun Man Wong, Pui Ying Choy, Qingyang Zhao, On Ying Yuen, Chung Chiu Yeung, Chau Ming So, Fuk Yee Kwong
Summary: A new series of hemilabile benzimidazolyl phosphines are easily assembled and prepared on a large scale via a simple one-pot procedure. X-ray crystallographic analyses demonstrate that the Pd metal center can coordinate in different fashions depending on the size of the -PRz group. Ligands with a -PCyz moiety are more efficient in expediting aromatic C-C bond-coupling reactions, while those with a -P-t-Bu-z group promote C-N bond-forming reactions.
Article
Chemistry, Physical
Chau Ming So, On Ying Yuen, Shan Shan Ng, Zicong Chen
Summary: This study presents a general chemoselective Suzuki-Miyaura coupling using a Pd/L33 catalyst, showing efficient coupling of polyhalogenated aryl triflates by controlling reactivity order and key factors, achieving high yields and chemoselectivity with low Pd catalyst loading.
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, Organic
On Ying Yuen, Chau Ming So
Summary: This article discusses the recent development of gamma-arylation of alpha,beta-unsaturated carbonyl compounds and presents the ligand-controlled, site-selective alpha- and gamma-arylation of alpha,beta-unsaturated carbonyl ketones with (hetero)aryl halides. The site selectivity of the reaction can be switched by simply changing the phosphine ligand.
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, 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, 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).
Article
Chemistry, Organic
Man Pan Leung, Chung Chiu Yeung, Pui Ying Choy, Chau Ming So, Fuk Yee Kwong
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2020)
Review
Chemistry, Multidisciplinary
Chauming So, Onying Yuen, Fukyee Kwong, Chihchiang Chen, Chengchao Pai, Raymond Waiyin Sun
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE
(2020)
Article
Chemistry, Organic
Hang Wai Lee, Chau Ming So, On Ying Yuen, Wing Tak Wong, Fuk Yee Kwong
ORGANIC CHEMISTRY FRONTIERS
(2020)