Article
Chemistry, Organic
Suna Han, Xin Shen, Xiaoxue Wu, Chaochao Xie, Guofu Zi, Guohua Hou
Summary: In this study, a Cu-catalyzed highly diastereo- and enantioselective methylboration reaction of diverse heterocyclic compounds was realized for the first time. The reaction provides the corresponding organoboron compounds bearing two adjacent chiral centers with excellent diastereoselectivities and enantioselectivities. This method offers an efficient and highly enantioselective approach for the synthesis of chiral organoboron compounds and their derivatives containing heterocyclic structures.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Ming Li, Guo-Qing Sun, Yu-Yu Liu, Shun-Xi Li, Hai-Chao Liu, Yi-Feng Qiu, Dong-Pin Chen, Xi-Cun Wang, Yong-Min Liang, Zheng-Jun Quan
Summary: A nickel-catalyzed three-component tandem radical cyclization reaction was developed to synthesize gamma-lactam-substituted allene derivatives from aryl bromides, 1,3-enynes, and aryl boric acids. This strategy allowed the lactam alkyl radicals generated through the cyclization process to participate in multicomponent coupling, leading to the direct conversion of 1,3-enynes into poly substituted allene compounds. The method demonstrated wide substrate scope and provided a series of 1,5-difunctionalized allenes in a one-pot reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ze-Liang He, Yi Zhang, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Summary: This study reports a three-component auto-tandem reaction catalyzed by palladium, which efficiently constructs a variety of organic compounds. The reaction demonstrates high chemo- and regioselectivity, achieving 1,3,4-trifunctionalization of the 1,3-enyne motif.
Article
Chemistry, Multidisciplinary
Hiroaki Iwamoto, Yu Ozawa, Yuta Takenouchi, Tsuneo Imamoto, Hajime Ito
Summary: The new C-2-symmetrical P-chirogenic bisphosphine ligand, (R,R)-5,8-TMS-QuinoxP*, exhibited higher reactivity and enantioselectivity in the direct enantioconvergent borylation of cyclic allyl electrophiles. The silyl groups on the ligand backbone were found to play a crucial role in the interlocking structures and in improving reactivity through entropy effects. Detailed calculations also indicated significant enantioselective recognition of carbon-carbon double bonds in the borylation process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Luo Ge, Syuzanna R. Harutyunyan
Summary: Chiral bisphosphine ligands play a key role in transition-metal-catalyzed asymmetric synthesis. However, the commonly used transition metals are expensive and scarce, and the synthesis of chiral phosphine ligands is complex. In this study, a catalytic asymmetric hydrophosphination reaction using a chiral complex of earth-abundant manganese(i) was developed. This reaction provides a short and efficient synthetic route to access easily obtainable and structurally tunable chiral bisphosphines, which can be used in asymmetric catalysis with earth-abundant metal-based organometallic catalysts.
Article
Chemistry, Multidisciplinary
Lei Wang, Wenxin Lu, Jiwu Zhang, Qinglei Chong, Fanke Meng
Summary: In this study, an unprecedented cobalt-catalyzed regio-, diastereo- and enantioselective hydrosilylation of 1,3-dienes is presented, enabling the simultaneous construction of a carbon- and a silicon-stereogenic center. The generated chiral silanes exhibit high efficiency and stereoselectivity, and can be further functionalized to obtain valuable chiral building blocks.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Ulysse Caniparoli, Imma Escofet, Antonio M. Echavarren
Summary: Planar chiral monodentate 1,3-disubstituted ferrocene phosphines inspired by JohnPhos-type ligands have been synthesized and applied for the enantioselective gold(I) catalyzed [4 + 2] cycloaddition of 1,6-arylenynes. Computational studies elucidated the working mode of the catalyst, involving attractive noncovalent interactions that induce the folding of the substrate in the chiral environment of the ligand.
Article
Multidisciplinary Sciences
Bo-Ran Wang, Yan-Bo Li, Qi Zhang, Dingding Gao, Ping Tian, Qinghua Li, Liang Yin
Summary: A copper(I)-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides and 1,3-enynes is reported, providing chiral poly-substituted pyrrolidines with high selectivities. 4-aryl-1,3-enynes and 4-silyl-1,3-enynes are suitable dipolarophiles, while 4-alkyl-1,3-enynes are inert. The method is capable of constructing tetrasubstituted stereogenic carbon centers and chiral spiro pyrrolidines. DFT calculations suggest a concerted mechanism. Transformations starting from the pyrrolidine bearing a triethylsilylethynyl group and centered on the alkyne group are achieved.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Christopher J. C. Cooze, Wesley McNutt, Markus D. Schoetz, Bohdan Sosunovych, Svetlana Grigoryan, Rylan J. Lundgren
Summary: Metal-catalyzed enantioselective conjugate additions are reliable methods for stereoselective synthesis, but multicomponent reactions initiated by conjugate arylation of acyclic pi-systems are rare. This study demonstrates a new Rh-catalyst system that allows highly enantioselective conjugate addition reactions of electron-deficient 1,3-dienes, generating Z-homoallylic alcohols with three stereocenters. The reaction products exhibit high diastereoselectivity and optical purity, enabling the synthesis of compounds with multiple stereocenters.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Melina C. Ontivero, Teodoro S. Kaufman, Ivan Cortes, Andrea B. J. Bracca
Summary: A new, facile, and efficient method for synthesizing methoximes from aromatic aldehydes and ketones was reported, using environmentally friendly MnCl2.4H(2)O as a catalyst. The method achieved good to excellent yields under mild conditions, without the need for additional ligands.
ROYAL SOCIETY OPEN SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Shang-Hai Yu, Tian-Jun Gong, Yao Fu
Summary: A cooperative Cu/Pd-catalysed borylallenylation of 2-trifluoromethyl-1,3-enynes with propargylic carbonates under mild reaction conditions was developed, providing facile and efficient access to conjugated bisallenes with a broad range of functional groups.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
In-Soo Myeong, Nadide Hazal Avci, Mohammad Movassaghi
Summary: The first total synthesis of (-)-kopsifoline A and (+)-kopsifoline E was achieved in this study, featuring a biogenetically inspired regioselective C17-functionalization strategy for a versatile intermediate. The vinylogous urethane substructure of the intermediate allowed for the synthesis of (-)-kopsifoline D via C3-C21 bond formation under Mitsunobu reaction conditions, as well as selective C17-functionalization en route to (-)-kopsifoline A and (+)-kopsifoline E.
Article
Chemistry, Organic
Melanie A. Drew, Andrew J. Tague, Christopher Richardson, Stephen G. Pyne, Christopher J. T. Hyland
Summary: A two-step Pd-catalyzed (3 + 2) cycloaddition/HNO2 elimination reaction sequence has been developed to efficiently produce novel cyclic 1,3-dien-5-yne systems with high atom efficiency. The research allows for the selective isolation of a single diastereoisomer of the cycloadduct, demonstrating the potential for practical applications in organic synthesis.
Article
Chemistry, Multidisciplinary
Ya Chen, Junjie Wang, Yixin Lu
Summary: In this study, we combine photoredox catalysis and copper catalysis for the first time to achieve radical 1,4-carbocyanations of 1,3-enynes. By utilizing alkyl N-hydroxyphthalimide esters as radical precursors, the mild and redox-neutral protocol shows broad substrate scope and remarkable functional group tolerance. This strategy enables the synthesis of diverse multi-substituted allenes with high chemo- and regio-selectivities, allowing late stage allenylation of natural products and drug molecules.
Article
Chemistry, Organic
Qijian Ni, Xuyang Wang, Da Zeng, Qianling Wu, Xiaoxiao Song
Summary: By using a chiral bifunctional squaramide catalyst, an asymmetric [3+3] cyclization of nitroenynes and 3-pyrrolyloxindoles has been achieved, providing an efficient access to enantioenriched polycyclic aza-spirooxindoles with 32-95% isolated yields and excellent stereocontrol under mild reaction conditions.
