Article
Chemistry, Organic
Congcong Yin, Yingmin Pan, Longsheng Zheng, Bijin Lin, Jialin Wen, Xumu Zhang
Summary: Enantioselective hydrogenation of imines via an outer-sphere mechanism was achieved using an iridium tridentate catalyst, resulting in high enantioselectivities and turnover numbers up to 10,000. This method was successfully applied in the synthesis of chiral amines with an alpha-stereocenter, allowing for the preparation of cinacalcet with remarkably high enantioselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Haibo Wu, Hao Su, Erik J. Schulze, Bram B. C. Peters, Mark D. Nolan, Jianping Yang, Thishana Singh, Marten S. G. Ahlquist, Pher G. Andersson
Summary: The study presents a highly efficient desymmetrization of 1,4-dienes through iridium-catalyzed site- and enantioselective hydrogenation, allowing the installation of two adjacent stereogenic centers. High yields and excellent selectivities were achieved for a range of substrates, and the methodology was demonstrated by synthesizing key intermediates of natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Pep Rojo, Medea Molinari, Albert Cabre, Clara Garcia-Mateos, Antoni Riera, Xavier Verdaguer
Summary: Chiral compounds containing nitrogen heteroatoms are crucial for the chemical, pharmaceutical, and agrochemical industries. In this study, a series of P-stereogenic phosphinooxazoline iridium catalysts were synthesized and successfully used in the asymmetric hydrogenation of N-Boc-2,3-diarylallyl amines, achieving high enantioselectivity. The synthetic utility of the obtained 2,3-diarylpropyl amines was also demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Jordan L. Harper, Stephanie Felten, Ryan M. Stolley, Alexander S. Hegg, Paul H-Y Cheong, Janis Louie
Summary: The mechanistic investigation into the origins of regio- and chemoselectivities observed in iron/pyridine dialdimine (PDAI)-catalyzed intermolecular [2+2+2] cycloaddition reactions of terminal alkynes and cyanamides reveals the significant role of the hemilabile PDAI ligand in controlling the observed selectivity of the resultant products.
Article
Chemistry, Multidisciplinary
Alexia N. Kim, Aurapat Ngamnithiporn, Michael D. Bartberger, Brian M. Stoltz
Summary: The first asymmetric trans-selective hydrogenation of 1,3-disubstituted isoquinolines has been developed, resulting in enantioenriched trans-tetrahydroisoquinolines in good yield with high enantioselectivity. Mechanistic studies reveal the crucial role of non-coordinating chlorinated solvents and halide additives in enabling trans-selectivity.
Article
Chemistry, Multidisciplinary
Tao Liu, Xin-Rui Mao, Shuo Song, Zi-Yang Chen, Yichen Wu, Li-Ping Xu, Peng Wang
Summary: Here, the first example of Ni-catalyzed asymmetric hydrosilylation of 1,1-disubstituted allenes with high level of regioselectivities and enantioselectivities is reported. The development of SPSiOL-derived bisphosphite ligands (SPSiPO) was crucial for achieving this stereoselective hydrosilylation reaction. This protocol offers a versatile method for constructing enantioenriched tertiary allylsilanes in a straightforward and atom-economic manner, with broad substrate scope and excellent functional group and heterocycle tolerance.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tianjiao Hu, Lukas Lueckemeier, Constantin Daniliuc, Frank Glorius
Summary: The direct enantioselective hydrogenation of 2-quinolones using Ru(II)-NHC catalyst has been achieved, providing alkyl-, aryl- and halogen-substituted optically active dihydro-2-quinolones in high yields with moderate to excellent enantioselectivities. This reaction presents an efficient and atom-economic pathway to construct simple chiral 3,4-dihydro-2-quinolones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Dongxu He, Donghao Wang, Chen Xu, Xiangyou Xing
Summary: A highly efficient kinetic resolution of allylic alcohols with Z/E mixtures was achieved via Ru-catalyzed selective dehydrogenation. Not only were allylic alcohols obtained with pure Z-geometry, but the corresponding selectivity factors rank among the few highest for kinetic resolution reported in the literature.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Lu Qian, Xixia Tang, Yulei Wang, Guixia Liu, Zheng Huang
Summary: The use of a chiral (NCP)Ir complex as the precatalyst allows for the asymmetric transfer hydrogenation of diaryl ketones. This method is applicable to various ortho-substituted diaryl ketones and can be conducted in gram scale under mild reaction conditions.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jose A. Carmona, Patricia Rodriguez-Salamanca, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An atroposelective Ir-catalyzed dynamic kinetic resolution (DKR) of 2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes is achieved by transfer hydrogenative coupling of allyl acetate. The reaction leads to the installation of central and axial chirality, with high diastereoselectivities and excellent enantioselectivities when ortho-cyclometalated iridium-DM-BINAP is used as the catalyst. The racemization of the substrates is facilitated through a designed transient Lewis acid-base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Josep Mas-Rosello, Christopher J. Cope, Eric Tan, Benjamin Pinson, Alan Robinson, Tomas Smejkal, Nicolai Cramer
Summary: Cyclometalated cyclopentadienyl iridium(III) complexes are efficient catalysts in the hydrogenation of oximes, with alkoxy-substituted aryl ketimine ligands providing the best catalytic performance. The stable iridium C,N-chelation is crucial for the catalytic activity, and the hydrogenation system demonstrates high functional group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zi-Xuan Wang, Bi-Jie Li
Summary: This study reports an amide-directed, regiodivergent, and enantioselective hydroalkynylation reaction. The regioselectivity can be tuned by choosing appropriate ligands, leading to the formation of products with acyclic tertiary or quaternary stereocenters beta to an amide. Furthermore, an asymmetric conjugated alkynylation reaction was achieved through a sequence of alkene isomerization and regioselective hydroalkynylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Wei Zhao, Wenji Wang, Huan Zhou, Qishan Liu, Zhiqing Ma, Haizhou Huang, Mingxin Chang
Summary: A one-pot asymmetric hydrogenation of pyridines with subsequent N-alkylation using a traceless Bronsted acid activation strategy is reported. The reaction exhibits high stereoselectivity and can be used to synthesize indolizidines and quinolizidines. Experimental and theoretical studies reveal that chloride anion and noncovalent interactions play important roles in determining the stereoselectivity of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Peng Lu, Hongliang Wang, Yihui Mao, Xin Hong, Zhan Lu
Summary: Investigation on asymmetric hydrogenation of olefins is vital for the synthesis of pharmaceutical molecules and chemical industry. A cobalt-catalyzed enantioconvergent hydrogenation method has been developed for common minimally functionalized E/Z-olefin mixtures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xiaoqing Wang, Yuqing Bai, Xiaoyong Zhai, Bo Wu, Yonggui Zhou
Summary: An environmentally sustainable copper-catalyzed dehydrocoupling polymerization method was developed for efficient preparation of poly(silyl ether)s (PSEs) with high yields and molecular weight. The PSEs exhibit good thermal stability and low glass-transition temperature.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Zhou-Hao Zhu, Yi-Xuan Ding, Yong-Gui Zhou
Summary: A novel transfer-catalyst-free biomimetic reduction method has been developed, which utilizes the chiral and regenerable [2.2]paracyclophane-based NAD(P)H model CYNAM to reduce tetrasubstituted olefins 3-sulfonyl coumarins, resulting in chiral 3-sulfonyl dihydrocoumarins with excellent enantioselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiao-Yong Zhai, Xiao-Qing Wang, Bo Wu, Yong-Gui Zhou
Summary: This study demonstrates a copper-catalyzed enantioselective insertion of carbene into Si-H bond applied to polycondensation, producing a new type of degradable polyesters. Thermogravimetric analysis indicates these polyesters exhibit good thermal stability.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Wen-Jun Huang, Zhi-Peng Chen, Li-Xia Liu, Yong-Gui Zhou, Bo Wu, Guo-Fang Jiang
Summary: A facile method for the synthesis of pyrrolo[2,3-j]phenanthridines from indoleanilines and aldehydes has been established, which features excellent yields, high efficiency and a wide range of substrate scope. Mechanism studies revealed that this reaction is a cascade process involving acid-catalyzed condensation, cyclization and oxidative aromatization.
JOURNAL OF HETEROCYCLIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Qing-Xian Xie, Li-Xia Liu, Zhou-Hao Zhu, Chang-Bin Yu, Yong-Gui Zhou
Summary: In this study, a ruthenium-catalyzed asymmetric transfer hydrogenation of 2,3-disubstituted flavanones was developed. The reaction allowed for the construction of three contiguous stereocenters under basic conditions through a combination of dynamic kinetic resolution and retro-oxa-Michael addition. This method provided chiral flavanols with excellent enantioselectivities and diastereoselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zilong Huang, Yuan He, Liandi Wang, Jiying Li, Bao-Hua Xu, Yong-Gui Zhou, Zhengkun Yu
Summary: A concise synthetic route to spiroindoline-fused S-heterocycles was developed using copper-catalyzed [4 + 1] annulation and enaminothiones as donor-acceptor synthons. The reaction showed good reactivity, broad substrate tolerance, and high yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Guangshou Feng, Colton K. Ku, Jiaqi Zhao, Qiu Wang
Summary: This paper reports an unprecedented three-component aminofluorination of alkenes and 1,3-dienes, which can achieve the synthesis of fi-fluoroalkylamines using innovative copper-catalyzed electrophilic amination strategy and alkylamine precursors. The method features high regioselectivity and good tolerance of various functional groups, providing a direct entry to a broad range of fi-fluorinated alkylamines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Xiang Li, Gao-Wei Wang, Li-Xia Liu, Chang-Bin Yu, Yong-Gui Zhou
Summary: Here, the authors describe the first example of palladium-catalyzed asymmetric hydrogenolysis of easily accessible aryl triflates for the construction of axially chiral biaryl scaffolds. The resulting chiral biaryl compounds were used to prepare axially chiral monophosphine ligands, which were further employed in palladium-catalyzed asymmetric allylic alkylation with excellent enantioselectivities and high branched and linear ratios, highlighting the potential utility of this methodology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tong Niu, Li-Xia Liu, Bo Wu, Yong-Gui Zhou
Summary: A series of [2,2]paracyclophane-based tridentate PNO ligands with planar chirality were designed and synthesized. These easily prepared chiral tridentate PNO ligands were successfully applied to the iridium-catalyzed asymmetric hydrogenation of simple ketones, providing chiral alcohols with high efficiency and excellent enantioselectivities (up to 99% yield and >99% ee). Control experiments demonstrated the indispensability of both N-H and O-H in the ligands.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zilong Huang, Jie Lin, Mingrui Li, Zhengkun Yu, Yong-Gui Zhou
Summary: A zinc(II)-catalyzed [2+2+1] annulation reaction of internal alkenes, diazooxindoles, and isocyanates was developed for the efficient synthesis of multisubstituted spirooxindoles. This multi-component transformation involves the in situ formation of a sulfur-containing spirocyclic intermediate, followed by a 1,3-dipolar addition reaction of the intermediate with the internal alkene, resulting in a formal [2+2+1] annulation in a one-pot manner. The synthetic protocol utilizes a low-toxicity main group metal catalyst, readily available reagents, and provides high yields of up to 96% for the synthesis of multisubstituted spirooxindole derivatives.
Review
Chemistry, Multidisciplinary
Xiao Xiao, Kaini Xu, Zhong-Hua Gao, Zhou-Hao Zhu, Changqing Ye, Baoguo Zhao, Sanzhong Luo, Song Ye, Yong-Gui Zhou, Senmiao Xu, Shou-Fei Zhu, Hongli Bao, Wei Sun, Xiaoming Wang, Kuiling Ding
Summary: Enzymes are essential for biological transformations and have attracted great attention for their structures and functions. Biomimetic chemistry has rapidly developed in response to the demand for bioactive molecules and efficient synthesis. Biomimetic asymmetric catalysis, inspired by enzymes, has been recognized as one of the most promising strategies for producing valuable chiral compounds. This review summarizes the evolution of biomimetic asymmetric catalysis in terms of biomimetic design, catalyst development, and catalytic transformations, providing insights into bridging the gap between bio-catalysis and chemical synthesis.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Zheng Liu, Sheng-Mei Lu, Bao-Qian Zhao, Hao-Dong Chen, Mu-Wang Chen, Yong-Gui Zhou
Summary: A method using zinc chloride was developed to purify compounds with pyridine structure from Mitsunobu reaction mixtures, and a sulfide anion was used to release bipyridines from Ullmann coupling reaction mixtures by competitively coordinating the copper ion. These improvements enabled the facile synthesis of the chiral 2,2'-bipyridine ligand (R-a,S,S)-C3-ACBP, achieving an overall yield of 48% at a 7 gram scale within 3-4 days without column chromatography.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Li-Xia Liu, Yu-Qing Bai, Xiang Li, Chang-Bin Yu, Yong-Gui Zhou
Summary: Combining base-promoted retro-sulfa-Michael addition with palladium-catalyzed asymmetric allenylic alkylation, a streamlined synthesis of chiral thiochromanones containing two central chiralities (including a quaternary stereogenic center) and an axial chirality (allene unit) was successfully achieved, with yields up to 98%, dr of 49.0:1, and >99% ee.
Article
Chemistry, Organic
Wen-Jun Huang, Li-Xia Liu, Yong-Gui Zhou, Bo Wu, Guo-Fang Jiang
Summary: We report a Bronsted acid-catalyzed C6 functionalization of 2,3-disubstituted indoles with 2,2-diarylacetonitriles for efficient construction of cyano-substituted all-carbon quaternary centers with excellent yields. The synthetic utility was demonstrated by the conversion of the cyano-group which enables the divergent preparation of aldehydes, primary amines and amides. Control experiments suggested that this process involves C-H oxidation of 2,2-diarylacetonitriles to in situ generate d,d-disubstituted p-quinone methide intermediates. This protocol provides an efficient method for C6 functionalization of 2,3-disubstituted indoles to construct all-carbon quaternary centers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Yuan He, Zilong Huang, Kaikai Wu, Juan Ma, Yong-Gui Zhou, Zhengkun Yu
Summary: C-H functionalization is an effective method for establishing carbon-carbon and carbon-heteroatom bonds, and has made significant progress. Transition-metal-catalyzed carbene insertion to C-H bonds is one of the hot research topics in this field, with various catalyst design strategies and synthetic methods. This review summarizes the research progress up to July 2021 and discusses future directions.
CHEMICAL SOCIETY REVIEWS
(2022)
