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, Organic
Paz Yepes, Angel L. Suarez-Sobrino, Miguel A. Rodriguez, Alfredo Ballesteros
Summary: The regio- and stereoselective carbosilylation reaction of tosylynamides with allylic trimethylsilanes is efficiently catalyzed by TMSNTf2 or HNTf2, resulting in high yields of (Z)-α-allyl-P-trimethylsilylenamides. Theoretical calculations reveal that the C-C triple bond of the ynamides is activated by the trimethylsilylium ion, leading to the formation of a P-trimethylsilylketenimonium cation. The subsequent transformations of the products demonstrate the synthetic utility of this reaction.
Article
Chemistry, Multidisciplinary
Swetha Jos, Connor Szwetkowski, Carla Slebodnick, Robert Ricker, Ka Lok Chan, Wing Chun Chan, Udo Radius, Zhenyang Lin, Todd B. Marder, Webster L. Santos
Summary: A transition metal-free, regio- and stereo-selective, phosphine-catalyzed method for the synthesis of (E)-1-boryl-1,3-enynes has been reported in this paper. The reaction proceeds with high selectivity for boron addition to the external carbon of the 1,3-diyne framework.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Lucas Pages, Maxime Bouquin, Florian Jaroschik, Florian Monnier, Marc Taillefer
Summary: We present a simple protocol for the copper-catalyzed hydrothiolation of N-unsaturated precursors, enabling the room-temperature transformation of thiols into various thioethers and thioaminals with good selectivity. The use of a low loading of commercially available Cu(CH3CN)(4)PF6 catalyst facilitates the process.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kazuyuki Torii, Atsushi Kawakubo, Xianjin Lin, Tetsuaki Fujihara, Tatsuo Yajima, Yasushi Obora
Summary: A highly regioselective and stereoselective difunctionalization reaction of 1,3-diene with amine and disilane has been developed, which can form C-N and C-Si bonds in a one-step process. This method shows high Z-selectivity and can be scaled up to 100 g, making it suitable for industrial applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Kazuyuki Torii, Kazuki Tabaru, Yasushi Obora
Summary: This Letter presents a regioselective and Z-selective three-component silylalkoxylation of 1,3-diene via the use of various alcohols, disilane, and a catalytic Pd/Cu/1,4-benzoquinone/O-2 system. The method allows the synthesis of tetra-substituted allyl silanes containing allyl ether moieties in up to 80% isolated yield on a scale of 1-10 mmol, with a wide range of substrates suitable for use in the reaction system.
Article
Chemistry, Organic
Yunfei Sha, Jiandong Liu, Liang Wang, Demin Liang, Da Wu, Hegui Gong
Summary: This study presents a facile method for constructing 1,3-dienes by cross-electrophile coupling of two open-chain vinyl halides, with moderate chemoselectivities observed between terminal bromoalkenes and internal vinyl bromides. The mild method is tolerant of various functional groups and can be applied to the total synthesis of solanone, a tobacco fragrance compound.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jin-Tao Ma, Tianze Zhang, Bo-Ying Yao, Li-Jun Xiao, Qi-Lin Zhou
Summary: We present a enantioselective nickel-catalyzed borylative coupling of 1,3-dienes with aldehydes, providing a one-step efficient synthesis of highly valuable homoallylic alcohols. The reaction involves 1,4-carboboration of dienes leading to the formation of C-C and C-B bonds and the construction of two continuous stereogenic centers. The diastereoselectivity of the reaction can be controlled by the choice of (Z)-1,3-dienes or (E)-1,3-dienes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Pierre Hansjacob, Frederic R. Leroux, Vincent Gandon, Morgan Donnard
Summary: The palladium-catalyzed silylcyanation of ynamides is highly selective, producing exclusively tetrasubstituted 2-aminoacrylonitriles derivatives. The stereoselectivity is directly controlled by the nature of the substituent at the beta-position of the ynamide. The reaction is tolerant of various functional groups and provides a general method to access fully substituted 2-aminoacrylonitriles. The mechanism of this intriguing transformation is elucidated by computational study, and the range of 2-aminoacrylonitriles is expanded through postfunctionalization using the newly installed vinylsilane functionality.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Swetha Jos, Christine Tan, Pierre Thilmany, Alaa Saadane, Carla Slebodnick, Gwilherm Evano, Webster L. Santos
Summary: We have reported a tri-n-butyl phosphine catalyzed hydroboration reaction of ynamides, which provides regio- and stereo-selective formation of (Z)-beta-borylenamides in good yields. Surprisingly, a formal cis addition to the triple bond was observed, and this finding was confirmed by NMR and X-ray crystallography. P-31 NMR studies suggest that a zwitterionic vinylphosphonium intermediate plays a key role in the reaction mechanism. Furthermore, the resulting products were successfully transformed into beta-CF3 enamides via stereoretentive trifluoromethylation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Zhihao Guo, Huanan Wen, Guixia Liu, Zheng Huang
Summary: The regio- and stereoselective hydrosilylation of 1,3-enynes with primary and secondary silanes to access 1,3-dienylsilanes using an iron precatalyst with IPO ligand demonstrates mild conditions, broad substrate scope, and good functional group tolerance. The synthetic utility of the reaction was further validated by gram-scale reactions and subsequent transformations.
Article
Chemistry, Organic
Rongrong Yu, Yidan Xing, Xianjie Fang
Summary: A regio-, chemo-, and enantioselective nickel-catalyzed hydrocyanation of 1,3-dienes has been achieved by using a specific multichiral diphosphite ligand. Besides aryl-substituted 1,3-dienes, challenging aliphatic 1,3-diene substrates can also be selectively converted to the corresponding 1,2-adducts with high yields and the highest enantioselectivities to date.
Article
Chemistry, Organic
Yuanjiu Xiao, Lei Tang, Tong-Tong Xu, Jian-Jun Feng
Summary: An atom-economical protocol for the efficient and highly selective trans-hydroarylation of ynamides with hydroxyarenes has been developed using B(C6F5)3 as the catalyst. This approach offers the advantages of readily available starting materials, low catalyst loading, mild reaction conditions, a broad substrate scope, ease of scale-up, and versatile functionalizations of the enamide products.
Article
Chemistry, Multidisciplinary
Ling Liao, Ying Zhang, Zhong-Wei Wu, Zhong-Tian Ye, Xue-Xin Zhang, Guangying Chen, Jin-Sheng Yu
Summary: A highly enantio- and regio-selective method for Markovnikov hydrofluoroalkylation of 1,3-dienes was developed using nickel catalysis. This is the first catalytic asymmetric hydrofluoroalkylation of olefins. The method demonstrated broad substrate scope, mild reaction conditions, excellent enantio- and regio-selectivity, and the ability to access diverse fluorinated building blocks.
Article
Chemistry, Organic
Hannah Siera, Mathis Kreuzahler, Christoph Woelper, Gebhard Haberhauer
Summary: Transition metal catalysis is a useful tool for C-C bond-forming reactions. Here, it is shown that gold(I)-catalyzed hydroalkynylation can selectively produce ynenamides, a relatively unknown type of molecule.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yoshihiro Oonishi, Akihito Hosotani, Takayuki Yokoe, Yoshihiro Sato
Article
Chemistry, Organic
Ryohei Doi, Taichi Okano, Iman Abdullah, Yoshihiro Sato
Review
Chemistry, Multidisciplinary
Tsuyoshi Mita, Yoshihiro Sato
CHEMISTRY-AN ASIAN JOURNAL
(2019)
Article
Chemistry, Multidisciplinary
Takahisa Taniguchi, Nozomi Saito, Ryohei Doi, Arato Kimoto, Naoyuki Hoshiya, Katsumasa Fujiki, Satoshi Shuto, Hiromichi Fujioka, Mitsuhiro Arisawa, Yoshihiro Sato
Article
Chemistry, Applied
Tsuyoshi Mita, Masashi Uchiyama, Yoshihiro Sato
ADVANCED SYNTHESIS & CATALYSIS
(2020)
Article
Chemistry, Organic
Toshiki Akiyama, Yuki Wada, Makito Yamada, Yasunori Shio, Tetsuo Honma, Shuhei Shimoda, Kazuki Tsuruta, Yusuke Tamenori, Hitoshi Haneoka, Takeyuki Suzuki, Kazuo Harada, Hayato Tsurugi, Kazushi Mashima, Jun-ya Hasegawa, Yoshihiro Sato, Mitsuhiro Arisawa
Article
Chemistry, Physical
Ryohei Doi, Koji Shimizu, Yuma Ikemoto, Masashi Uchiyama, Mikiko Koshiba, Atsushi Furukawa, Katsumi Maenaka, Satoshi Watanabe, Yoshihiro Sato
Summary: This study reports a nickel-catalyzed cascade reaction to construct a 3-acylbenzo[b]furan skeleton. Through reaction condition optimization, the catalyst loading could be reduced to 5-10 mol %, leading to the synthesis of various functionalized compounds. Stoichiometric study of nickel complexes and DFT calculations were conducted to support a possible reaction mechanism.
Article
Chemistry, Multidisciplinary
Ryohei Doi, Kanako Hayashi, Yoshihiro Sato
Summary: In this study, palladium-catalyzed decarboxylative alpha-polyfluoroarylation of ketones was reported. By screening reaction conditions, XPhos and Ruphos were selected as ancillary ligands for Pd(0) catalysts, enabling the reaction to be applied to various substrates. A cross-over experiment was conducted to gain insight into the reaction mechanism.
Article
Chemistry, Organic
Yoshihiro Oonishi, Shunki Sakamoto, Shuya Agata, Yoshihiro Sato
Summary: In the Rhodium(I)-catalyzed enantioselective cyclization of enynes, the presence of different functional groups on the substrate molecules affects the structure and yield of the products, with C(sp(3))-H bond activation being an important high energy barrier step in the cyclization reaction.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Souta Misawa, Asaki Miyairi, Yoshihiro Oonishi, Steven P. Nolan, Yoshihiro Sato
Summary: Polarized alkynes such as ynol ethers and ynamides undergo Au(I)-catalyzed hydroalkoxylation/Claisen rearrangement cascade reactions with allylic alcohols, proceeding under mild conditions with high regioselectivity. The resulting gamma,delta-unsaturated esters or amides are formed in an atom-economical manner using the [Au(IPr)NTf(2)] catalyst.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Applied
Yoshihiro Oonishi, Kazuki Takagishi, Yi-Min Liu, Yoshihiro Sato
Summary: This article describes the rhodium-catalyzed enantioselective hydroacylation of racemic alkynals with a substituent at the alpha-position of the carbonyl group. The reaction can be applied to a wide range of substrates (22 examples), and mechanistic studies reveal a dynamic kinetic resolution (DKR) process during the hydroacylation, leading to various cyclic ketones with yields of 47-93% and enantiomeric ratios (er) of 59:41 to 97:3 from racemic starting materials.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Koji Yamada, Kaho Ishizawa, Yoshihiro Oonishi, Yoshihiro Sato, Takahide Nishi
Summary: This study presents a practical synthetic method for accessing oxazolidinone-2,3-fused indoline and azaindoline derivatives through one-pot cyclization. These derivatives, which contain sp3-hybridized carbons, could serve as novel scaffolds in medicinal chemistry.
Article
Chemistry, Organic
Mikiko Koshiba, Yuto Furuki, Kazuhiro Morisaki, Ryohei Doi, Yoshihiro Sato
Summary: We report a nickel-catalyzed migratory cycloisomerization reaction for the synthesis of 2,3-disubstituted indoles. The reaction proceeds via acyl transfer on the nitrogen atom of the substrate to the C3 position in the product, and a suitable N-heterocyclic carbene ligand is used in the reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Asaki Miyairi, Yoshihiro Oonishi, Yoshihiro Sato
Summary: This study successfully demonstrated the one-pot synthesis of fully substituted 2-aminofurans via a gold-catalyzed cascade reaction, under highly mild conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Ryohei Doi, Yoshihiro Sato
NICKEL CATALYSIS IN ORGANIC SYNTHESIS: METHODS AND REACTIONS
(2020)