Article
Chemistry, Multidisciplinary
Wei Sun, Meng-Yang Hu, Zhan-Sheng Lu, Ming-Yao Huang, Xin-Yu Zhang, Shou-Fei Zhu
Summary: This article reports a method for stereoselective transformation using an iron catalyst to synthesize Z-allylsilanes with high regioselectivity and exclusive stereoselectivity from E/Z mixtures. The mechanism of this reaction differs from previously reported mechanisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Weisi Guo, Qian Wang, Jieping Zhu
Summary: This study reports a highly chemo- and regio-selective 1,2-aminoisothiocyanation reaction of 1,3-dienes using N-aminopyridinium salts and TMSNCS under mild photoredox catalytic conditions. The selective formation of products is attributed to the facile isomerization of allyl thiocyanates to allyl isothiocyanates under photocatalytic conditions, offering potential applications in the synthesis of allyl isothiocyanates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xiaoyu Wu, Wei Liu, Liqun Yang, Yue Wang, Tianwen Liu, Yao Yuan, Yan Lu, Zhaoguo Zhang
Summary: In this study, a regioselective hydrosilylation reaction using a nickel catalyst was developed. By adjusting the temperature and ligands, homoallylic and allylic silanes could be efficiently generated with excellent yields and regioselectivities.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jiantao Zhang, Weiming Zhu, Peng Zhou, Cui Chen, Weibing Liu
Summary: A catalyst-free 1,2-difunctionalization of 1,3-dienes with CHCl3 and TBHP in the presence of NEt3 has been developed, giving the desired dichloromethylhydroxylation products. Various substituents on the aryl ring were tolerated and moderate to good yields of the corresponding products were obtained. When Na2CO3 was used as the base, the formation of the key α-amino radical was inhibited, resulting in the formation of 1,2-peroxyhydroxylation products. This method provides an effective and functional group tolerant strategy for diene 1,2-difunctionalization, allowing for further functionalization and modification of synthetic molecules.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Yichen Ji, Sai Praneet Batchu, Ajibola Lawal, Dionisios G. Vlachos, Raymond J. Gorte, Stavros Caratzoulas, Omar A. Abdelrahman
Summary: ZrO2 exhibits high selectivity (>90%) in the dehydra-decyclization of C-5 cyclic ethers to form conjugated pentadienes, even at high conversions. It predominantly produces 1,3-pentadiene from both 2-methyltetrahydrofuran and tetrahydropyran, and nearly stoichiometric amounts of isoprene from 3-methyltetrahydrofuran. Other catalysts show lower selectivity and produce a mixture of diene isomers. ZrO2 has the ability to catalytically convert ring-opened intermediates to conjugated alkenolates, which selectively dehydrate to form conjugated dienes.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Sanghyup Seo, Joonho Jung, Hyunwoo Kim
Summary: Novel P, O-type ligands, N-disulfonyl bicyclic bridgehead phosphorus triamides, exhibited high reactivity in Pd-catalyzed hydrosilylation reactions involving tertiary silanes, unactivated alkenes, and conjugated dienes. The use of these ligands significantly improved the regioselectivity of diene hydrosilylation towards 1,2-hydrosilylation. Experimental and computational studies confirmed the bidentate nature of the ligand and provided insights into the reaction mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Subham Pradhan, Subramanian Thiyagarajan, Chidambaram Gunanathan
Summary: An efficient and selective catalytic method for the partial reduction of aldazines using a ruthenium catalyst has been developed, resulting in the exclusive formation of N-boryl-N-benzyl hydrazone products from symmetrical aldazines with mono-hydroboration and desymmetrization. The mechanism involves the in situ formation of an intermediate, indicating the involvement of [{(eta(6)-p-cymene)RuCl}2(mu-H-mu-Cl)] (1a) in the selective hydroboration.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yonghong Liu, Huaipu Yan, Yuqing Chen, Erjun Hao, Lei Shi
Summary: This study describes a highly efficient method for the photoinduced copper-catalyzed 1,2-amino oxygenation of 1,3-dienes. The approach involves the use of a single copper catalyst, which serves as both a photosensitizer and a reactant with allyl radicals through single electron transfer (SET) processes. The method enables the synthesis of a variety of quaternary carbon-centered allyl carboxylic esters and tertiary ethers with high yields and excellent regioselectivity under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Degong Kong, Bowen Hu, Min Yang, Haiping Xia, Dafa Chen
Summary: Two types of regio- and stereoselective hydrosilylation reactions of 1,3-enynes catalyzed by Co complexes have been developed. Dppf-CoCl2 is suitable for 3,4-hydrosilylation of 4-aryl-substituted 1,3-enynes, while Xantphos-CoCl2 is applicable for 4,3-hydrosilylation of 4-alkyl-substituted 1,3-enynes. Various functional groups are tolerated in the reactions, and the resulting 1,3-dienylsilanes can participate in several valuable transformations.
Article
Chemistry, Inorganic & Nuclear
Dinmukhamed Shakhman, Anton Dmitrienko, Melanie Pilkington, Georgii I. I. Nikonov
Summary: A novel bidentate amine-imine ligand precursor LH has been synthesized and reacted with ZnMe2 to generate the zinc methyl complex LZnMe (4). Compound 4 is a catalyst for the hydroboration and hydrosilylation of N-heterocycles, but with moderate catalytic activity. A more active catalyst, the zinc hydride complex LZnH (5), was synthesized and it catalyzes the selective 1,2-hydroboration of nitrogen heteroaromatics under mild conditions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Qifeng Jiang, Alexandra F. Gittens, Sydnee Wong, Maxime A. Siegler, Rebekka S. Klausen
Summary: In this study, we report a new method for the addition reaction between cyclosilanes and aryl acetylenes. The resulting organosilanes exhibit visible light absorption properties and can serve as important building blocks for the synthesis of novel conjugated polymers.
Article
Chemistry, Inorganic & Nuclear
Xinzhe Shi, Sihan Li, Anke Spannenberg, Fabian Reiss, Torsten Beweries
Summary: The study of new structures and reactivity patterns in organic and organometallic chemistry is of great interest. Metallacycles of electropositive transition metals provide an excellent platform for this purpose. In this work, a set of ring-strained group 4 ansa-metallocene-based 1-metallacyclobuta-2,3-dienes were synthesized and their reactivity towards carbodiimides was studied. The results showed that the biradical character of these species depends on the metal as well as the nature of the cyclopentadienyl ligands.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Zi-Lu Wang, Ying Wang, Jian-Lin Xu, Meng Zhao, Kai-Yang Dai, Cui-Cui Shan, Yun-He Xu
Summary: Novel copper-catalyzed regiodivergent hydrosilylation reactions have been developed, allowing highly selective control of 1,2- and 1,4-hydrosilylation reactions of substituted 1,3-dienes by varying the catalytic systems. Additionally, the first successful 1,4-hydrosilylation reaction of 2-aryl-substituted 1,3-dienes with diphenylsilane was achieved, providing convenient and efficient methods for synthesizing structurally diverse allylsilanes.
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)
Review
Chemistry, Physical
Geoffrey Dumonteil, Sabine Berteina-Raboin
Summary: This review focuses on commonly used synthetic methods to obtain molecules with conjugated dienes. The methods discussed mainly involve cross-coupling reactions using metals such as nickel, palladium, ruthenium, cobalt, cobalt/zinc, manganese, zirconium, or iron. Through examples, the review explores the synthesis of natural molecules or their analogues. Specifically, the total synthesis of the phytohormone Acid Abscisic (ABA) by the author's team is discussed, which involves the development of a conjugated diene chain.
