Article
Chemistry, Multidisciplinary
Xin He, Pengchen Ma, Yuhai Tang, Jing Li, Shenyu Shen, Martin J. Lear, K. N. Houk, Silong Xu
Summary: We report a phosphine-catalyzed (3 + 2) annulation of cyclopropenones with various electrophilic pi systems, yielding products including butenolides, butyrolactams, maleimides, and iminomaleimides in high yields with a wide range of substrates. An alpha-ketenyl phosphorous ylide is identified as the key intermediate, which undergoes preferential catalytic cyclization with aldehydes. This phosphine-catalyzed activation of cyclopropenones provides a versatile C-3 synthon for formal cycloadditon reactions.
Article
Chemistry, Organic
Barry M. Trost, Zhijun Zuo, Youliang Wang
Summary: The study presents a highly regio-, diastereo-, and enantioselective TMM cycloaddition reaction for the rapid assembly of 2-acyl-methylenecyclopentane in an atom-economic fashion. This intermolecular protocol provides easy and divergent access to a variety of structurally attractive cyclic adducts. The choice of a robust chiral diamidophosphite ligand, developed by the research group, was crucial for the success of this transformation.
Article
Chemistry, Multidisciplinary
Jacqueline Bitai, Alastair J. Nimmo, Alexandra M. Z. Slawin, Andrew D. Smith
Summary: A new method for the enantioselective synthesis of substituted vinylcyclopentanes has been developed using cooperative palladium and isothiourea catalysis. Functionalized cyclopentanes can be synthesized with good yields and stereocontrol by intermolecular cycloaddition between reactive intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Song Feng, Baoqi Ren, Lige Li, Fengmin Xia, Zhiyong Tang, Yu Zhang, Xiaoning Liu, Qixuan Lu, Wenge Zhong
Summary: This method achieves the N-heteroaryl-directed Ru-catalyzed asymmetric hydrogenation of α,α-disubstituted vinyl ethers with good to excellent enantioselectivities, providing an attractive approach for synthesizing pharmaceutically active heteroaryl compounds containing chiral ether units.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Hiroto Uno, Koki Kawai, Taichi Araki, Motoo Shiro, Norio Shibata
Summary: Gem-difluoromethylene moieties are attractive in medicinal chemistry due to their ability to mimic other more ubiquitous functional groups. A novel asymmetric method for their construction was developed, allowing easy access to chiral 1,3-dioxanes that contain a tetrasubstituted difluoroalkyl stereogenic center. The gem-difluoro substitution pattern promotes the reaction, and various substrates were suitable for this method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jingjing Geng, Deli Sun, Yanhong Song, Weiqi Tong, Fan Wu
Summary: This study presents a nickel-catalyzed enantioconvergent reductive cross-coupling reaction between alpha-chlorosulfones and vinyl bromides, enabling the enantioselective construction of chiral allylic sulfones. The mild reaction conditions demonstrate excellent functional group compatibility, as evidenced by a broad substrate scope and tolerance of complex bioactive molecules.
Article
Chemistry, Organic
Rui-Hao Liu, Guo-Li Chai, Xiao Wang, Hong-Yu Deng, Junbiao Chang
Summary: The asymmetric 1,3-dipolar cycloaddition reaction of beta-trifluoromethyl alpha,beta-unsaturated ketone with N,N'-cyclic azomethine imines was developed using a (R)-3,3'-(3,5-(CF3)2-C6H3)2-BINOL-boron complex catalyst. The reaction efficiently produces N,N'-bicyclic pyrazolidine derivatives with a stereogenic carbon center containing CF3 motifs in high yields and excellent diastereo- and enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Li Lin, Mei Wang, Jiawei Zhou, Fei Li, Huiyun Liu
Summary: The direct C2 addition of 5H-oxazol-4-ones to gamma-keto-alpha,beta-unsaturated esters catalyzed by a chiral squaramide has been achieved, resulting in diverse highly functionalized gamma-keto esters with a C2-oxazolone at the alpha-position in high yields and excellent stereoselectivities (d.r. > 20:1 and up to 98% ee).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yang Gao, Phil S. Baran
Summary: A new approach to the enantiocontrolled synthesis of alpha-amino ketone derivatives is presented using a decarboxylative acylation strategy. This method yields the desired alpha-amido ketones with good yield and high enantioselectivity when an acyl chloride and an alpha-amido-containing redox-active ester are exposed to a nickel catalyst, chiral ligand, and metal reductant. The reaction has wide substrate scope, scalability, and simplifies the synthesis of known structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Li-Guo Lu, Jun-Hua Chen, Xiao-Bo Huang, Miao-Chang Liu, Yun-Bing Zhou, Hua-Yue Wu
Summary: The Pd-catalyzed selective ring opening reaction of cyclopropenones with vinyl epoxides allows for the synthesis of a wide range of conjugated alkadienyl carboxylates in good yield and excellent regioselectivity. This study demonstrates the new application of zwitterionic pi-allyl palladium intermediates in organic synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Can Gao, Xunhua Wang, Jitian Liu, Xiaoxun Li
Summary: This study presents a palladium-catalyzed asymmetric [4 + 4] cycloaddition, allowing for efficient synthesis of highly stereochemically controlled nitrogen-heterocyclic compounds. The method provides good regio-, stereo-, and enantioselectivity, with the ability to tolerate complex substrates derived from natural products.
Article
Chemistry, Organic
Jin Zhou, Chen Chen, Qiwen Pang, Wei-Fang Zuo, Xiang Li, Gu Zhan, Qian-Qian Yang, Bo Han
Summary: A series of multifunctional dihydroquinolinone frameworks were synthesized through synergistic catalysis combining photolysis and Lewis base catalysis utilizing in situ generated ketenes from the visible-light-mediated Wolff rearrangement of alpha-diazoketones and ortho-amino MBH carbonates. This powerful [4 + 2] annulation further expands the application of MBH carbonates in cooperative catalysis and shows good compatibility and high efficiency. Furthermore, control experiments indicate that synergistic catalysis strategy plays a crucial role in the cycloaddition reaction, and a plausible mechanism is proposed to explain the reaction process.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Applied
Roman Ottenbacher, Vladimir Kurganskiy, Evgenii P. Talsi, Konstantin P. Bryliakov
Summary: In this study, we reported the enantioselective epoxidation of electron-deficient cis- and trans-alpha,beta-unsaturated amides using the environmentally benign oxidant H2O2. The manganese complexes with bis-amino-bis-pyridine and related ligands as catalysts showed high efficiency and excellent chemo- and enantioselectivity. The presence of NH moiety was found to enhance the enantioselectivity and yield of cis-enamides epoxidation significantly.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Dmitri Trubitson, Jevgenija Martonova, Marina Kudrjasova, Kristin Erkman, Ivar Jarving, Tonis Kanger
Summary: An efficient enantioselective organocatalytic method has been developed for the synthesis of N-alkylated indoles with alpha-branched alkyl substituents from unsaturated indolyl ketones via a Michael addition. The resulting products exhibit high enantioselectivities and good yields, with tolerance towards various nucleophiles and substitution patterns of the indole ring. Both electron-withdrawing and electron-donating substituents can be accommodated at any position of the heteroaromatic ring.
Article
Chemistry, Multidisciplinary
Haifeng Zheng, Kan Wang, Luca De Angelis, Hadi D. Arman, Michael P. Doyle
Summary: An oxocarbenium-olefin cross metathesis occurs during Bronsted acid catalyzed reactions of 1H-isochromene acetals with vinyl diazo compounds, leading to diverse products controlled by reactant substituents. Polysubstituted benzobicyclo[3.3.1] oxocines, benzobicyclo[3.2.2]oxepines, benzobicyclopropane, and naphthalenes are obtained in good to excellent yields and selectivities, shedding light on the oxocarbenium-olefin metathesis/rearrangement process and the origin of substituent-dependent selectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Cheng Xu, Zhen Ye, Li Xiang, Shuhan Yang, Qian Peng, Xuebing Leng, Yaofeng Chen
Summary: The synthesis of silacycle compounds, including the insertion of metal-substituted silylene fragments into the aromatic ring of naphthalene, is of both fundamental and application importance. This insertion is followed by interesting rearrangements to yield silaspiro-benzocycloheptenyl and cyclobutenosilaindan derivatives, with mechanistic aspects revealed through DFT investigations. Additionally, formed cyclobutenosilaindan potassium can readily react with various compounds to afford substituted cyclobutenosilaindans in high yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Huan Zhang, Enhui Wang, Shasha Geng, Zhengli Liu, Yun He, Qian Peng, Zhang Feng
Summary: The iron-catalyzed defluorosilylation reaction is an efficient, highly functional-group compatible, and stereo- and regioselective reaction that can be used for late-stage silylation of biologically relevant compounds, offering opportunities for applications in medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Bin Lu, Xinyi Liang, Jinyu Zhang, Zijian Wang, Qian Peng, Xiaoming Wang
Summary: This study reports a three-component reaction enabled by dirhodium(II)/Xantphos catalysis to efficiently synthesize diverse alpha-quaternary alpha-amino acid derivatives. Mechanistic studies indicate that the transformation is achieved through a relay dirhodium(II)-catalyzed carbene insertion and allylic alkylation process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Lei Kang, Yongjia Lin, Zeng Gao, Jinlong Zhang, Huameng Yang, Jinlong Qian, Qian Peng, Gaoxi Jiang
Summary: The fluorine substituents activate C-C and C-S bonds through antiphase orbital interaction, leading to alpha-elimination. The rate-limiting step involves four-membered transition states with ring strain. Sterically eclipsed repulsion and secondary orbital interaction influence the stereoselectivity.
Article
Chemistry, Multidisciplinary
Yu-Hao Huang, Yichen Wu, Zile Zhu, Sujuan Zheng, Zihang Ye, Qian Peng, Peng Wang
Summary: This study demonstrated an asymmetric synthesis method for monohydrosilanes via intramolecular hydrosilylation strategy, with high diastereo-, regio-, and enantioselectivities, including chiral oxasilacycles. The catalyst loading could be reduced to 0.1 mol %, making it one of the most efficient methods for accessing chiral monohydrosilanes. Mechanistic studies suggest a Chalk-Harrod mechanism for the Rh-catalyzed intramolecular asymmetric hydrosilylation reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shuai Huang, Gao-Peng Zhang, Yang-Jie Jiang, Fei-Le Yu, Chang-Hua Ding, Xue-Long Hou
Summary: This article presents a facile and efficient method for constructing vicinal tertiary and quaternary chiral carbon centers in synthetic chemistry. By using Kundig-type chiral N-heterocyclic carbene as the ligand, the reaction between Pd-catalyzed umpolung asymmetric allylic alkylation of hydrazones and monosubstituted allyl reagents achieves high yields and high selectivities.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Pusu Yang, Hui-Zhen Du, Xiang-Yu Zhang, Yong-Liang Xia, Jun-Tao Sun, Qian Peng, Bing-Tao Guan
Summary: This study reports the synthesis of phosphate ligated dialkyl yttrium complexes with high stability and a tunable ligand. These complexes exhibit high activity and selectivity in the catalytic polymerization of isoprene, with the ability to switch stereoselectivity by using an additive.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Organic
Juan Wang, Yun-Fan Li, Juan Du, Shuai Huang, Chang-Hua Ding, Henry N. C. Wong, Xue-Long Hou
Summary: Alkynyl esters can undergo palladium-catalyzed asymmetric (3 + 2) cycloaddition with vinyl epoxides, leading to the formation of chiral dihydrofurans with high yields and high enantiomeric excess values when a chiral benzylic substituted P,N-ligand is used. The synthetic method has also been demonstrated for the synthesis of 2,3-cis-tetrahydrofuran.
Article
Chemistry, Physical
Ke Chen, Hongdan Zhu, Yuling Li, Qian Peng, Yinlong Guo, Xiaoming Wang
Summary: The switchable semireduction of alkynes to (Z)- or (E)-alkenes catalyzed by a dinuclear cobalt complex supported by a macrocyclic bis pyridyl diimine (PDI) ligand allows control of the stereoisomerization process by adjusting the amount of water, providing a convenient method for obtaining either (Z)- or (E)-olefin isomer in a single transformation.
Article
Chemistry, Multidisciplinary
Bin Feng, Hao-Yu Zhang, Hongling Qin, Qian Peng, Xuebing Leng, Yaofeng Chen
Summary: In this study, a rare-earth metal complex with a unique double-bond character was synthesized and found to catalyze the hydrogenation of terminal alkenes under mild conditions. Isotopic labeling experiments indicated that the catalytic reaction proceeded through an addition/elimination mechanism rather than the traditional sigma-bond metathesis mechanism.
Article
Chemistry, Multidisciplinary
Qianchi Lin, Sujuan Zheng, Long Chen, Jin Wu, Jinzhao Li, Peizhi Liu, Shunxi Dong, Xiaohua Liu, Qian Peng, Xiaoming Feng
Summary: In this study, a highly enantioselective tandem reaction of alpha-alkynylketoamides with diarylphosphine oxides was achieved, leading to the synthesis of trisubstituted allenes with a diarylphosphinate functionality. The reaction showed broad substrate scope, high regio- and enantioselectivity, and good functional-group compatibility. The synthetic utility of the methodology was demonstrated by the conversion of products into complex bridged polycyclic architectures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Kairui Zhang, Yaya Wang, Hongdan Zhu, Qian Peng
Summary: Quasi-classical molecular dynamics is a computational method that combines classical molecular dynamics and electronic structure theory to simulate the statistics of products or intermediates in reaction mechanisms, as well as provide dynamic information on chemical bond formation/cleavage. Research on organic reaction mechanisms using quasi-classical molecular dynamics helps deepen understanding of these mechanisms and expand the theory of organic chemistry.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Zi-Ru Chen, Yu-Quan Zhu, Si-Min Xu, Yufei Zhao, Qian Peng, Hong Yan
Summary: In this study, LDH-based photocatalysts were investigated for their different transportation routes of electrons and holes in order to suppress unwanted photo-induced electron-hole recombination. The carrier mobilities of electrons and holes in LDHs were calculated using deformation potential theory and Marcus theory, revealing that carriers can only move along certain facets to reduce recombination. Approaches for suppressing carrier recombination in LDH-based photocatalysts include decreasing the number of layers and adjusting the metal species in the LDH matrix.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Xia Zhong, Ziwei Zhong, Zhikun Wu, Zhen Ye, Yuxiang Feng, Shunxi Dong, Xiaohua Liu, Qian Peng, Xiaoming Feng
Summary: A new strategy of asymmetric carbonyl catalysis has been developed using a chiral Lewis acid-bonded aldehyde for the direct Mannich/condensation cascade reaction of glycine ester with aromatic aldimines. The co-catalytic system of 2-picolinaldehyde and chiral Yb-III-N,N '-dioxides was found to be efficient, providing trisubstituted imidazolidines in moderate to good yields with high diastereo- and enantioselectivities under mild conditions. Enantiodivergent synthesis was achieved by changing the sub-structures of the chiral ligands.
