- A preparation of benzylic and allylic boronates: Cross-coupling of aryl- and alkenylstannanes with bromomethylboronates
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Palladium catalyzed cross-coupling of aryl- or alkenylstannanes with pinacol and pinanediol bromomethylboronates affords the corresponding homologated benzylic or allylic boronates in moderate to good yields.
- Falck,Bondlela, Muralidhar,Ye, Jianhua,Su-Dong, Cho
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- Synthesis of benzylic boronates via palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron with benzylic halides
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The palladium cross-coupling reaction of benzyl halides with diboron 1 yielded structurally diverse pinacol benzylic boronates. Under these reaction conditions, sensitive functionalities such as esters and nitriles are tolerated and the benzylic boronates
- Giroux, André
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Read Online
- Practical Synthesis of Allyl, Allenyl, and Benzyl Boronates through SN1′-Type Borylation under Heterogeneous Gold Catalysis
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Efficient borylation of sp3 C-O bonds by supported Au catalysts is described. Au nanoparticles supported on TiO2 showed high activity under mild conditions employing low catalyst loading conditions without the aid of any additives, such as phosphine and bases. A variety of allyl, propargyl, and benzyl substrates participated in the heterogeneously catalyzed reactions to furnish the corresponding allyl, allenyl, and benzyl boronates in high yields. Besides, Au/TiO2 was also effective for the direct borylation of allylic and benzylic alcohols. A mechanistic investigation based on a Hammett study and control experiments revealed that sp3 C-O bond borylation over supported Au catalysts proceeded through SN1′-type mechanism involving the formation of a carbocationic intermediate. The high activity, reusability, and environmental compatibility of the supported Au catalysts as well as the scalability of the reaction system enable the practical synthesis of valuable organoboron compounds.
- Miura, Hiroki,Hachiya, Yuka,Nishio, Hidenori,Fukuta, Yohei,Toyomasu, Tomoya,Kobayashi, Kosa,Masaki, Yosuke,Shishido, Tetsuya
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p. 758 - 766
(2021/02/03)
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- Visible-light-driven graphene supported Cu/Pd alloy nanoparticle-catalyzed borylation of alkyl bromides and chlorides in air
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A highly efficient photocatalytic protocol for borylation of alkyl bromides and chlorides with graphene supported Cu/Pd alloy nanoparticles as a heterogeneous catalyst is reported. This photocatalytic system operates with visible light in air, providing a wide range of primary and secondary alkyl halides with B2pin2 or B2neop2 in high yields at low temperatures, thereby demonstrating its broad utility and functional group tolerance. The high performance is attributed to a synergistic effect of localized surface plasmon resonance (LSPR) of Cu and charge transfer from Cu to Pd due to the alloy surface charge heterogeneity. Transfer of energetic electrons from Pd to electrophilic alkyl halides lead to the formation of the alkyl radicals, which quickly react with a nucleophilic adduct of a diboron compound with base adsorbed on the positively charged Cu sites to form the corresponding borylation product.
- Jiao, Zhi-Feng,Tian, Ya-Ming,Guo, Xiao-Ning,Radius, Udo,Braunschweig, Holger,Marder, Todd B.,Guo, Xiang-Yun
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p. 258 - 265
(2021/02/16)
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- Photochemical Radical C–H Halogenation of Benzyl N-Methyliminodiacetyl (MIDA) Boronates: Synthesis of α-Functionalized Alkyl Boronates
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α-Haloboronates are useful organic synthons that can be converted to a diverse array of α-substituted alkyl borons. Methods to α-haloboronates are limiting and often suffer from harsh reaction conditions. Reported herein is a photochemical radical C-H halogenation of benzyl N-methyliminodiacetyl (MIDA) boronates. Fluorination, chlorination, and bromination reactions were effective by using this protocol. Upon reaction with different nucleophiles, the C?Br bond in the brominated product could be readily transformed to a series of C?C, C?O, C?N, C?S, C?P, and C?I bonds, some of which are difficult to forge with α-halo sp2-B boronate esters. An activation effect of B(MIDA) moiety was found.
- Yang, Ling,Tan, Dong-Hang,Fan, Wen-Xin,Liu, Xu-Ge,Wu, Jia-Qiang,Huang, Zhi-Shu,Li, Qingjiang,Wang, Honggen
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supporting information
p. 3454 - 3458
(2020/12/17)
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- Metal-Free Direct Deoxygenative Borylation of Aldehydes and Ketones
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Direct conversion of aldehydes and ketones into alkylboronic esters via deoxygenative borylation represents an unknown yet highly desirable transformation. Herein, we present a one-step and metal-free method for carbonyl deoxy-borylation under mild conditions. A wide range of aromatic aldehydes and ketones are tolerated and successfully converted into the corresponding benzylboronates. By the same deoxygenation manifold with aliphatic aldehydes and ketones, we also enable a concise synthesis of 1,1,2-tris(boronates), a family of compounds that currently lack efficient synthetic methods. Given its simplicity and versatility, we expect that this novel borylation approach could show great promise in organoboron synthesis and inspire more carbonyl deoxygenative transformations in both academic and industrial settings.
- Huang, Chia-Yu,Li, Chao-Jun,Li, Jianbin,Qiu, Zihang,Wang, Haining
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supporting information
p. 13011 - 13020
(2020/09/01)
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- IMMUNOPROTEASOME INHIBITORS
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Provided herein are compounds, such as a compound of Formula (I), or a pharmaceutically acceptable salt thereof, that are immunoproteasome (such as LMP2 and LMP7) inhibitors. The compounds described herein can be useful for the treatment of diseases treatable by inhibition of immunoproteasomes. Also provided herein are pharmaceutical compositions containing such compounds and processes for preparing such compounds.
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Paragraph 0506
(2019/06/13)
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- Regioselective α-benzylation of 3-iodoazetidine via Suzuki cross-coupling
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An efficient protocol for the synthesis of α-benzyl azetidines starting from benzylboronic acid pinacol ester derivatives and 3-iodoazetidine was developed. A wide range of α-benzyl azetidine derivatives were obtained in moderate to good yields with high regioselectivity (>99%).
- Qiu, Zhenjiang,Zhu, Mingxiang,Zheng, Lu,Li, Jingya,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
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supporting information
p. 1321 - 1324
(2019/04/25)
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- Structure-based development of (1-(3′-Mercaptopropanamido)methyl)boronic Acid Derived Broad-Spectrum, Dual-Action Inhibitors of Metallo- And Serine-β-lactamases
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The emergence and spread of bacterial pathogens acquired metallo-β-lactamase (MBL) and serine-β-lactamase (SBL) medicated β-lactam resistance gives rise to an urgent need for the development of new dual-action MBL/SBL inhibitors. Application of a pharmacophore fusion strategy led to the identification of (2′S)-(1-(3′-mercapto-2′-methylpropanamido)methyl)boronic acid (MS01) as a new dual-action inhibitor, which manifests broad-spectrum inhibition to representative MBL/SBL enzymes, including the widespread VIM-2 and KPC-2. Guided by the VIM-2:MS01 and KPC-2:MS01 complex structures, further structural optimization yielded new, more potent dual-action inhibitors. Selectivity studies indicated that the inhibitors had no apparent inhibition to human angiotensin-converting enzyme-2 and showed selectivity across serine hydrolyases in E. coli and human HEK293T cells labeled by the activity-based probe TAMRA-FP. Moreover, the inhibitors displayed potentiation of meropenem efficacy against MBL- or SBL-positive clinical isolates without apparent cytotoxicity. This work will aid efforts to develop new types of clinically useful dual-action inhibitors targeting MBL/SBL enzymes.
- Wang, Yao-Ling,Liu, Sha,Yu, Zhu-Jun,Lei, Yuan,Huang, Meng-Yi,Yan, Yu-Hang,Ma, Qiang,Zheng, Yang,Deng, Hui,Sun, Ying,Wu, Chengyong,Yu, Yamei,Chen, Qiang,Wang, Zhenling,Wu, Yong,Li, Guo-Bo
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p. 7160 - 7184
(2019/08/28)
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- Method for synthesizing alkylborate compound
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The invention discloses a method for synthesizing an alkylborate compound, and concretely relates to a method for synthesizing the alkylborate compound through a cross-coupling reaction of chloralkaneand bis(pinacolato)diboron in the presence of metallic magnesium with Fe(acac)3 (acac = an acetylacetonate group) as a single component catalyst. The method for synthesizing the alkylborate compoundavoids the use of sensitive metal organic solvents and multi-component catalysts, realizes bilateral utilization of the bis(pinacolato)diboron, greatly reduces the use amount of the bis(pinacolato)diboron, and allows the coupling reaction of the cheap and easily-available chloralkane to be smoothly carried out under mild conditions; and compared with methods reported in literatures, the method disclosed in the invention has a better atom economy, a same or higher catalysis efficiency and a wider substrate applicability.
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Paragraph 0028
(2018/05/01)
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- Preparation method of benzyl boron ester compound
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The invention discloses a preparation method of a benzyl boron ester compound. According to the preparation method, aromatic boric acid Ar-B(OH)2, trimethyl silicon-based diazomethane, pinacol and tetrabutyl ammonium fluoride are subjected to a reaction in an organic solvent so as to obtain a benzyl pinacol boron ester compound, wherein Ar represents a non-heterocyclic aromatic group. After the method is adopted, the benzyl boron ester compound is obtained by starting from the aromatic boric acid and converting under a one-pot condition; the method is mild in reaction conditions, the reaction related to the method occurs smoothly in the air without needing strict water-free and oxygen-free conditions, and the method is convenient and simple to operate; the method has better tolerance and universality for functional groups and does not need an expensive metal catalyst and a ligand, thus being lower in reaction cost and being widely used for preparing the benzyl boron ester compound.
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Paragraph 0070; 0071; 0072; 0073; 0074; 0075
(2017/06/02)
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- Making Dimethylamino a Transformable Directing Group by Nickel-Catalyzed C-N Borylation
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The dimethylamino (Me2N) group is arguably the most versatile functional group capable of highly efficient and site-selective directed aromatic functionalizations at the ortho-, meta-, and para-positions depending on reaction conditions. While the repertoire of Me2N-directed reactions is growing at a rapid pace, the lack of a general method to transform this group to other functionalities hampers its wider application in organic synthesis. Here we report nickel-catalyzed C-N borylations of aryl- and benzyl-dimethylamines that permit the conversion of a huge library of largely underutilized Me2N-containing organic molecules into various functional molecules by taking advantage of the wealth of existing C-B functionalization methods.
- Zhang, Hua,Hagihara, Shinya,Itami, Kenichiro
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p. 16796 - 16800
(2015/11/16)
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- Iron-catalyzed borylation of alkyl electrophiles
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The use of low-cost iron(III) acetoacetate (Fe(acac)3) and tetramethylethylenediamine (TMEDA) enables the direct cross-coupling of alkyl halides with bis(pinacolato)diboron. This approach allows for the borylation of activated or unactivated primary, secondary, and tertiary bromides. Moreover, even the borylation of benzylic or allylic chlorides, tosylates, and mesylates are possible. The reactions proceed under mild conditions at room temperature and show broad functional-group compatibility and "robustness" as measured by a modified Glorius robustness screen.
- Atack, Thomas C.,Lecker, Rachel M.,Cook, Silas P.
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supporting information
p. 9521 - 9523
(2014/07/22)
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- Transition-metal-free synthesis of pinacol alkylboronates from tosylhydrazones
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Highly efficient: Pinacol alkylboronates were synthesized by the reaction of tosylhydrazones with bis(pinacolato)diboron or pinacolborane under transition-metal-free conditions. This reaction represents an expeditious conversion of carbonyl functionality into a boronate group. Copyright
- Li, Huan,Wang, Long,Zhang, Yan,Wang, Jianbo
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p. 2943 - 2946
(2012/04/18)
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- Palladium nanoparticle catalysis: Borylation of aryl and benzyl halides and one-pot biaryl synthesis via sequential borylation-Suzuki-Miyaura coupling
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Palladium nanoparticles generated in PEG catalyze the reaction of bis(pinacolato)diboron with various aryl/benzyl halides to afford aryl/benzyl boronates in high yield. Arylboronates thus prepared, have been directly used in the Suzuki-Miyaura coupling reaction with different aryl halides and benzyl halides in a convenient one-pot, two-step solvent free green synthesis of unsymmetrical biaryls and diarylmethanes. The Royal Society of Chemistry 2012.
- Bej, Ansuman,Srimani, Dipankar,Sarkar, Amitabha
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experimental part
p. 661 - 667
(2012/05/04)
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- Chemoselective Suzuki coupling of diborylmethane for facile synthesis of benzylboronates
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The chemoselective Pd-catalyzed Suzuki-Miyaura cross-coupling reaction using a diborylmethane is reported. The use of an equimolar amount of base with a diborylmethane realized chemoselective coupling for the synthesis of various benzylboronate derivatives. Sterically hindered aryl bromides can give products in moderate to excellent yields.
- Endo, Kohei,Ohkubo, Takahiro,Shibata, Takanori
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supporting information; experimental part
p. 3368 - 3371
(2011/09/12)
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- NITROGEN-CONTAINING HETEROARYL COMPOUNDS HAVING HIV INTEGRASE INHIBITORY ACTIVITY
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A compound of the formula (I): wherein Z4, Z5 and Z9 each is independently carbon atom or nitrogen atom; Y is hydroxy, mercapto or amino; RA is a group of the formula: (wherein C ring is nitrogen-containing heteroaryl) has an inhibitory activity against integrase.
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- Palladium-catalyzed benzylic C-H borylation of alkylbenzenes with bis(pinacolato)diboron or pinacolborane
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Borylation at the benzylic C-H bond of alkylbenzenes with bis(pinacolato)diboron [(Me4C2O2)B-B(O2C2Me 4)] or pinacolborane [(Me4C2O2)B-H] was carried out at
- Ishiyama, Tatsuo,Ishida, Kousaku,Takagi, Jun,Miyaura, Norio
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p. 1082 - 1083
(2007/10/03)
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