Article
Multidisciplinary Sciences
Zi-Lu Wang, Qi Li, Meng-Wei Yang, Zhao-Xin Song, Zhen-Yu Xiao, Wei-Wei Ma, Jin-Bo Zhao, Yun-He Xu
Summary: A copper-catalyzed ligand-controlled selective 1,2- and 1,4-hydrosilylation of 1,3-enynes was reported, which achieved enantiomerically enriched propargyl- and 1,2-allenylsilane products in high yields and excellent enantioselectivities. The reaction showed broad substrate scope and excellent regioselectivities, with mechanistic studies revealing the importance of allenylcopper as the reactive intermediate and the role of ligand in controlling the regioselectivity switch. The high enantiocontrol in the 1,4-hydrosilylation was also explained by DLPNO-CCSD(T) calculations.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Wei-Dong Zhang, Jia-Yu Zou, Qin Zhong, Shi-Sen Li, Jian Zhao
Summary: A simple and cost-effective Pd/Cu-catalyzed borylation of allenylic carbonates with B(2)Pin(2) was developed, providing high yields of 2-boryl 1,3-butadienes under mild conditions. Additionally, the use of different diboron reagents in the reaction was also demonstrated.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Malavath Ratanlal, Jayaram Vankudoth, Gangavaram V. M. Sharma, Maruti A. Mali, Bertrand Carboni, Fabienne Berree, Subhash Ghosh
Summary: An efficient stereo-controlled synthesis method using sequential Suzuki-Miyaura coupling reactions from easily prepared 1-alkene-1,2-diboronic esters and alkynyl bromides to obtain enyne and enediyne derivatives is reported. The resulting enyne boronic esters were further subjected to Borono-Mannich and Suzuki coupling reactions independently to obtain a,ss-unsaturated aminoester and tri-substituted olefin derivatives, respectively. Additionally, divergent syntheses of triazole and cyclopropylboronate derivatives were also presented.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Lucas Popek, Jorge Juan Cabrera-Trujillo, Vincent Debrauwer, Nicolas Blanchard, Karinne Miqueu, Vincent Bizet
Summary: This article describes a fully regio- and stereoselective hydroelementation reaction of SF5-alkynes with N, O, and S-nucleophiles, and the further functionalization of the resulting Z-(hetero)vinyl-SF5 intermediates. This reaction provides a suitable platform for accessing alpha-SF5 ketones and esters, as well as beta-SF5 amines and alcohols under mild reaction conditions. Experimental and computational comparative studies between SF5- and CF3-alkynes have been conducted to highlight and explain the observed differences in reactivity and selectivity between these two fluorinated motifs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Cai You, Mika Sakai, Constantin G. Daniliuc, Klaus Bergander, Shigehiro Yamaguchi, Armido Studer
Summary: The study introduces a catalyst-free 1,2-carboboration reaction of ynamides, which shows high yields with complete regio- and stereoselectivity, yielding valuable enamide compounds with synthetic potential.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Multidisciplinary
Yang Xi, Chenchen Wang, Qian Zhang, Jingping Qu, Yifeng Chen
Summary: This method efficiently synthesizes the chiral beta-fluoroaminated moiety with high enantioselectivity and exhibits the ability to transform the product into various vicinal benzylic fluoride derivatives with excellent stereo- and enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Meizhong Tang, Yongjiao Wei, Shenlin Huang, Lan-Gui Xie
Summary: This paper presents a simple synthesis method for the chemo-, regio-, and stereoselective preparation of beta-methylthio vinyl triflates by the reaction between alkynes and dimethyl(methylthio)sulfonium trifluoromethanesulfonate under neutral and extremely simple conditions.
Article
Chemistry, Organic
Stephen Collins, Joshua D. Sieber
Summary: In this study, we present an improved system for the Cu-catalyzed enantioselective reductive coupling of ketones and allenamides by optimizing the allenamide to prevent on-cycle rearrangement. High enantioselectivities were achieved for various ketones. Unlike cyclic allenamides, which favor the syn-form, the acyclic allenamides described in this work selectively generated anti-diastereomers. A rationalization for this change in diastereoselectivity is also provided.
Article
Chemistry, Organic
Dat Phuc Tran, Yuki Sato, Yuki Yamamoto, Shin-ichi Kawaguchi, Shintaro Kodama, Akihiro Nomoto, Akiya Ogawa
Summary: The study developed a method that can generate pentavalent and trivalent phosphorus-centered radicals simultaneously by homolytic cleavage of the P-V(O)-P-III bond, enabling the phosphinylphosphination of terminal alkynes. This method exhibits high regio- and stereoselectivity and can be applied to a wide range of terminal alkynes.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Tarek S. Mansour, Colleen A. Evans, David E. Bogucki, Sultan Chowdhury
Summary: Monobenzoylated 1,2-dithiane-4,5 diols undergo a novel ring contraction reaction under Mitsunobu conditions to produce 3,4-disubstituted 1,2-dithiolanes. This transformation is stereoselective and proceeds with retention of configuration. The yields for the trans isomers are higher than those of the cis series for a variety of O, N and S nucleophiles. A plausible pathway for forming the 1,2-dithiolanes involves the formation of a S-episulfonium intermediates.(c) 2023 Elsevier Ltd. All rights reserved.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Physical
Vivek Aryal, Lucas J. Chesley, Doleshwar Niroula, Rishi R. Sapkota, Roshan K. Dhungana, Ramesh Giri
Summary: We have disclosed a novel Ni-catalyzed alkylarylation reaction of electron-deficient alkenes, which allows the construction of two carbon-carbon bonds. The electron-deficient alkenes play a crucial role in stabilizing reaction intermediates and enhancing the catalytic rates. This reaction is also applicable to secondary alkylzinc reagents and internal alkenes, and exhibits excellent regio- and stereocontrol, leading to products with up to three contiguous all-carbon all-cis secondary stereocenters.
Article
Chemistry, Multidisciplinary
Wen-Bin Xu, Minghe Sun, Mouhai Shu, Changkun Li
Summary: In this study, alkynylphosphines were utilized as ligands in asymmetric metal catalysis for highly regio- and enantioselective allylic amination reactions. Chiral bis(oxazoline)alkynylphosphine ligands were synthesized and successfully employed in Rh-catalyzed reactions to produce chiral 1,2-disubstituted allylic amines with high yields and excellent enantioselectivity. The presence of a smaller linear alkynyl group on the phosphorus atom in the ligands played a crucial role in accommodating bulky 2-R' groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Multidisciplinary Sciences
Shubham Dutta, Shashank Shandilya, Shengwen Yang, Manash Protim Gogoi, Vincent Gandon, Akhila K. Sahoo
Summary: In this study, a palladium-catalyzed three-component coupling reaction was reported, enabling the selective regio- and stereoselective dicarbofunctionalization of unsymmetrical internal alkynes. This method shows broad applicability and tolerance towards labile functional groups, allowing the construction of diverse chemical structures.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Jian Han, Li-Li Zeng, Rong-Hui Huang, Xiao-Qing Feng, Fen-Er Chen
Summary: A concise and practical route for the hydrosulfonylation of alkynes using commercially available sulfonyl chlorides has been developed. The reaction conditions are mild and convenient, allowing the introduction of various functionalized sulfonyl groups into unactivated alkynes. The use of inexpensive manganese catalyst and common Xantphos ligand provides excellent control over the regio- and diastereoselectivities, resulting in efficient Cl-atom transfer.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)