Article
Chemistry, Organic
Sufal Paul, Piyush Kumar Verma, Anubhab Kashyap, Rahul Mondal, K. Geetharani
Summary: A new method has been developed for sequentially gem-thioborylating readily available aldehydes through cobalt-catalyzed diboration reaction. The N-heterocyclic carbene (NHC)-cobalt complex serves as a catalyst for the diboration of aldehydes to generate alpha-oxyl boronic esters, which react with lithium thiolates to form a tetracoordinate boronate species undergoing 1,2-metalate rearrangement in the presence of trifluoroacetic anhydride. The stepwise functionalization of the boryl and thiol moiety of the products enriches the chemical toolbox of diverse organic synthesis.
Review
Chemistry, Organic
Nanquan Jiang, Du Chen, Chao Liu
Summary: Organoboron compounds are important building blocks in synthetic chemistry due to their ability to transform C-B bonds. Alpha-oxylboronates, a special type of organoboronate, have geminal hydroxyl and boryl functionalities, which make them versatile reagents for chemical synthesis. This review mainly focuses on the synthesis and transformation of alpha-oxylboronates, particularly the transformations of their C-B and C-O bonds.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Yeosan Lee, Seungcheol Han, Seung Hwan Cho
Summary: Chemical and stereoselective transformations of polyborylalkanes are powerful methods to access optically active molecules efficiently. Gem-diborylalkanes, as versatile synthetic handles, can generate key intermediates for various enantioselective reactions. Catalytic reactions using gem-diborylalkanes can rapidly access diverse enantioenriched organoboron compounds for further transformations.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Wei-Cheng Zhao, Rui-Peng Li, Chao Ma, Qi-Ying Liao, Miao Wang, Zhi-Tao He
Summary: A novel protocol for stereoselective geminal bisglycosylations of saccharides has been established, showcasing the simultaneous introduction of C-C and C-B bonds at the anomeric stereogenic center of furanoses and pyranoses. Additionally, a scarce metal-free 1,1-difunctionalization process of alkenes has been demonstrated.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Gwanggyun Kim, Minjae Kim, Changsu Ryu, Juhyeok Choi, Seung Hwan Cho
Summary: We developed a transition-metal-free deborylative cyclization approach for the synthesis of enantioenriched cyclopropylboronates. Our method utilizes gamma-phosphate-containing gem-diborylalkanes derived from chiral epoxides and gem-diborylalkanes, enabling the synthesis of a broad range of enantioenriched cyclopropylboronates with excellent stereospecificity. The versatility of our approach was demonstrated through gram-scale reactions, and the enantioenriched tertiary cyclopropylboronates were successfully transformed into various enantioenriched cyclopropane derivatives using stereospecific boron-group transformations.
Article
Chemistry, Multidisciplinary
Jian-Jun Dai, Xin-Xin Teng, Wen Fang, Jun Xu, Hua-Jian Xu
Summary: An electrochemically promoted decarboxylative borylation reaction is reported, which can proceed under mild conditions without the use of transition metal- or photo-catalysts. The key feature of this reaction is the compatibility of diboron reagents with the electrochemical conditions. It exhibits broad substrate scope, good functional group tolerability, and easy scalability.
CHINESE CHEMICAL LETTERS
(2022)
Review
Chemistry, Multidisciplinary
Woohyun Jo, Jun Hee Lee, Seung Hwan Cho
Summary: This feature article summarises recent progress in the synthetic utilisation of alpha-borylcarbanions, including carbon-carbon bond formation with alkyl halides, alkenes, N-heteroarenes, and carbonyls. Carbon-boron bond formation in organohalides mediated by alpha-borylcarbanions is also summarised.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Tianhang Wang, Minyan Wang, Yandong Wang, Mingjie Li, Yuan Zheng, Qianwei Chen, Yue Zhao, Zhuangzhi Shi
Summary: This study reports a catalytic enantioselective hydroboration through desymmetrization of enantiotopic carbons in cyclopropanes. Treatment of cyclopropanes bearing an amide directing group with rhodium catalysis using HBpin as a boron source allows the construction of alkyl boronates containing γ-stereogenic amines. Ligand cooperativity of an exogenous chiral phosphite and an endogenous acetylacetonate plays a key role in achieving high enantioselectivity. Detailed experimental and computational studies elucidate the effect of ligand cooperativity and the key steps involved in the reaction.
Article
Chemistry, Multidisciplinary
Qiqiang Xie, Guangbin Dong
Summary: The Matteson-type reactions have gained increasing interest in organic synthesis, but current tactics mainly focus on carbon chains. In this study, we report the development of the oxa-Matteson reaction, which allows oxygen and carbenoid insertions into alkyl- and arylboronates, leading to the synthesis of boron-substituted ethers. The method demonstrates its utility in the preparation of functional ethers, asymmetric synthesis, and programmable construction of polyethers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Thorsten Kinsinger, Uli Kazmaier
Summary: The Matteson homologation is a versatile tool for the synthesis of polyunsaturated alkyl boronic esters, which can be used as precursors for constructing carbocycles. The high diversity of the Matteson reaction allows for the preparation of highly substituted cyclic boronic esters, suitable for further reactions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Shuo Yang, Wei-Tao Jiang, Bin Xiao
Summary: The study focused on tertiary cyclopropyl carbagermatranes obtained through zinc-mediated decarboxylation, which showed efficient reactivity in palladium-catalyzed cross-coupling reactions. They also exhibited orthogonal reactivity with boron reagents, acting as robust nucleophiles for the synthesis of tertiary cyclopropane and efficient intermediates for quaternary center formation.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Wei Sun, Yue Hu, Chungu Xia, Chao Liu
Summary: Gem-borylsilylalkanes have emerged as powerful reagents in synthetic chemistry due to their versatile transforming ability, and efforts have been made to access these motifs from easily accessible chemical feedstocks. Compared with gem-diborylalkane analogues, gem-borylsilylalkanes can be chemoselectively converted into various functionalized molecules through selective C-Si and C-B bond transformation.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Ryota Sakamoto, Minami Odagi, Atsuto Izumiseki, Kaname Konuki, Kazuo Nagasawa
Summary: In this study, we describe a versatile method for the synthesis of homoallenylboronic esters via lithiation-borylation and subsequent 1,2-rearrangement. The resulting homoallenylboronic esters can be successfully converted into Z- and E-1,3-dienes.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Juan Zhang, Shasha Geng, Zhang Feng
Summary: Organoboron and organosilane compounds are widely used in organic synthesis and pharmaceuticals. The functionalization of the C-F bond provides opportunities for the development of new medicinal compounds. Late-stage functionalization through defluoroborylation and defluorosilylation reactions shows promise in diversifying structures and creating new ideas for further research in this field.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Yuan Zhou, Tong Xiong, Li-Yan Zhou, Hong-Yan Li, You-Cai Xiao, Fen-Er Chen
Summary: This paper reports the catalytic asymmetric synthesis of borylated 3-hydroxyoxindoles by addition of gem-diborylalkanes to isatins. Chiral 3-hydroxyoxindoles bearing two contiguous stereogenic centers were produced with high stereoselectivity and demonstrated synthetic utility through transformations of the boryl moiety.
Article
Chemistry, Organic
Guy J. Clarkson, Stefan Roesner
Summary: An efficient methodology for the synthesis of benzofuropyridines and dibenzofurans from fluoropyridines or fluoroarenes and 2-bromophenyl acetates is presented. The streamlined one-pot procedure involves four-step directed ortho-lithiation, zincation, Negishi cross-coupling, and intramolecular nucleophilic aromatic substitution, enabling the easy assembly of a diverse set of fused benzofuro heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sheenagh G. Aiken, Joseph M. Bateman, Hsuan-Hung Liao, Alexander Fawcett, Teerawut Bootwicha, Paolo Vincetti, Eddie L. Myers, Adam Noble, Varinder K. Aggarwal
Summary: In this study, a highly efficient iterative strategy for the synthesis of polyacetates based on boronic ester homologation was reported. It does not require functional group manipulation between iterations. This methodology has been applied to the synthesis of bahamaolide A and has demonstrated versatility in various stereospecific transformations.
Article
Chemistry, Organic
Joseph C. Abell, Christian P. Bold, Laia Vicens, Tom Jentsch, Noelia Velasco Perez, Jasper L. Tyler, Robert N. Straker, Adam Noble, Varinder K. Aggarwal
Summary: Aza-spirocycles, highly rigid and three-dimensional structures, have been incorporated into pharmaceuticals due to their beneficial pharmacokinetic properties. We report a simple synthesis of spirocyclic dihydropyridines through an electrophile-induced dearomatization reaction, which offers the potential for rapid assembly of medicinally relevant spirocycles.
Letter
Hematology
Justin S. Trory, Attila Munkacsi, Kamila M. Sledz, Jordan Vautrinot, Lucy J. Goudswaard, Molly L. Jackson, Kate J. Heesom, Samantha F. Moore, Alastair W. Poole, Behnam Nabet, Varinder K. Aggarwal, Ingeborg Hers
Article
Chemistry, Multidisciplinary
Lydia I. Dewis, Madhavachary Rudrakshula, Christopher Williams, Elisabetta Chiarparin, Eddie L. Myers, Craig P. Butts, Varinder K. Aggarwal
Summary: Using α-helix mimetics as inhibitors of protein-protein interactions is a prevalent therapeutic strategy. Controlling the conformation of mimetics through destabilizing syn-pentane interactions can enhance their efficacy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Jasper L. Tyler, Varinder K. Aggarwal
Summary: The use of metalated (aza)bicyclo[1.1.0]butanes in synthesis is experiencing a revival, with numerous reports in the past 5 years demonstrating their ability to undergo unique transformations or generate novel fragments. These species have been found to participate in a wide range of reactions, facilitating rapid diversification of (aza)bicyclo[1.1.0]butane-containing compounds. The investigation into their reactivity has led to the elucidation of reaction mechanisms involving strained bicycles and will solidify their importance in organometallic chemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Organic
Varinder K. K. Aggarwal, Zuowei Xie, Hajime Ito
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ze-Shu Wang, Steven H. H. Bennett, Bilal Kicin, Changcheng Jing, Johan A. A. Pradeilles, Karen Thai, James R. R. Smith, P. David Bacos, Valerio Fasano, Carla M. M. Saunders, Varinder K. K. Aggarwal
Summary: In this study, a novel strategy for the construction of dihydrobenzofurans and indolines was described. The aromatic ring was created through an inverse-electron demand Diels-Alder reaction and a cheletropic extrusion sequence, followed by an aromatization process. The methodology was successfully applied in the total synthesis of the antiplatelet drug beraprost and the synthesis of functionalized indolines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Maryam Bashir, Muhammad Arshad, Robina Begum, Varinder K. Aggarwal
Summary: A highly selective asymmetric synthesis of a potent anti-TB drug (-)-bedaquiline was achieved through sulfur ylide asymmetric epoxidation, using (+)-isothiocineole as a chiral sulfide. The construction of the key diaryl epoxide exhibited excellent enantioselectivity (er 96:4) and diastereoselectivity (dr 90:10), followed by a highly regioselective ring opening (96:4). The synthesis was completed in nine steps starting from commercially available aldehyde with an overall yield of 8%.
Article
Chemistry, Multidisciplinary
Jingjing Wu, Chao Shu, Zhihang Li, Adam Noble, Varinder K. Aggarwal
Summary: This article describes a visible-light photoredox-catalyzed decarboxylative halogenation reaction using inexpensive inorganic halide salts as halogenating agents. Bromination with lithium bromide can be achieved using an organic photoredox catalyst under simple conditions, while chlorination requires dual photoredox-copper catalysis. The reaction exhibits excellent functional group tolerance and can convert structurally complex natural products into alkyl bromides and chlorides. Additionally, the method is also applicable to thiocyanation reactions with potassium thiocyanide for the synthesis of alkyl thiocyanates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kristian J. Chambers, Patthadon Sanghong, Daniel Carter Martos, Giorgia Casoni, Rory C. Mykura, Durga Prasad Hari, Adam Noble, Varinder K. Aggarwal
Summary: Enones are important functional groups in chemical synthesis and molecular biology. This study developed a one-pot strategy for the stereospecific conversion of boronic esters into enones using methoxyallene as a three-carbon building block. The methodology is versatile and has been successfully applied to the total synthesis of polyketide 10-deoxymethynolide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ruocheng Sang, Wangyujing Han, Hanwen Zhang, Carla M. Saunders, Adam Noble, Varinder K. Aggarwal
Summary: Copper catalysts can promote the dehydrogenative borylation of alkanes with bis(catecholato)diboron under oxidant-free conditions. This is due to the unexpected dual role of the copper catalyst, which promotes the oxidation of the diboron reagent and generates an electrophilic bis-boryloxide that acts as an effective borylating agent in subsequent redox-neutral photocatalytic C-H borylations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Santosh K. K. Pagire, Chao Shu, Dominik Reich, Adam Noble, Varinder K. K. Aggarwal
Summary: Carbon-phosphorus bond formation is important in synthetic chemistry due to the essential biochemical roles of phosphorus-containing compounds. However, the synthesis of aliphatic phosphonates through phosphonylation of alkyl radicals is rarely used. In this study, a phosphorus radical trap called BecaP is introduced, which enables efficient phosphonylation of alkyl radicals under visible light photocatalytic conditions. The ambiphilic nature of BecaP allows redox neutral reactions with both nucleophilic and electrophilic alkyl radical precursors. This method is applicable for late-stage installation of phosphonate motifs into medicinal agents and natural products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hong-Cheng Shen, Mihai V. Popescu, Ze-Shu Wang, Louis de Lescure, Adam Noble, Robert S. Paton, Varinder K. Aggarwal
Summary: We report an iridium-catalyzed asymmetric alkylation-induced 1,2-metalate rearrangement of bicyclo[1.1.0]butyl boronate complexes enabled by strain release. This method allows for the asymmetric difunctionalization of C-C bonds, including dicarbonation and carboboration, providing a variety of enantioenriched three-dimensional cyclobutane products. The diastereoselectivity of the reaction has been rationalized based on experimental data and density functional theory calculations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Correction
Chemistry, Organic
Sebastien Prevost, Karen Thai, Nina Schutzenmeister, Graeme Coulthard, William Erb, Varinder K. Aggarwal
