Article
Chemistry, Organic
Connor Szwetkowski, Carla Slebodnick, Webster L. Santos
Summary: A highly efficient and selective method has been developed for allenoate borylation, resulting in the synthesis of Z-beta,gamma-unsaturated beta-boryl esters. The method is performed under mild conditions and achieves high yields.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jiaming Liu, Ming Chen
Summary: A highly stereoselective synthesis of (E)-delta-boryl-anti-homoallylic alcohols has been developed in good yields with excellent E-selectivity. The E-vinylboronate group in the products provides a useful handle for cross-coupling reactions, as illustrated in the fragment synthesis of chaxamycins.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Shi-Sen Li, Qin Zhong, Jian Zhao
Summary: An efficient Cu-catalysed protoboration of allenyl-Bdans has been developed, leading to moderate to high yields of β-boryl allyl-Bdans with excellent regio- and stereoselectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Shangsheng Zhou, Yu Pu, Zhengli Liu, Xiaoming Zhang, Jiang Zhu, Zhang Feng
Summary: This study presents a novel iron-catalyzed reaction that efficiently converts unactivated gem-difluoroalkenes, gem-dichloroalkenes, and gem-dibromoalkenes into 1,2-bis(boryl)-alkanes with high selectivity and broad substrate applicability. Preliminary mechanistic studies suggest that double beta-F elimination plays a role in the catalytic cycle, with 1,1-diborylated alkenes potentially serving as intermediates in this iron-catalyzed 1,2-diborylation reaction.
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, Organic
Jinping Yuan, Pankaj Jain, Jon C. Antilla
Summary: The catalytic asymmetric addition of beta,gamma-substituted allylboronates to aldehydes has been described, showing highly efficient and selective reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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, Multidisciplinary
Fengxiang Zhu, Pengpeng Yin, Xiao-Feng Wu
Summary: A new Pd/Cu-catalyzed carbonylation and borylation reaction of alkynes with aryldiazonium salts has been developed, leading to the synthesis of alpha-unsubstituted beta-boryl ketones with complete regioselectivity. This transformation demonstrates broad substrate scope and excellent functional-group tolerance. The resulting 1,2-carbonylboration products offer opportunities for further transformations that cannot be achieved using known carbonylation procedures.
Article
Chemistry, Physical
Fang Zhou, Shaolin Zhu
Summary: Here, a chiral selective nickel-hydride catalyzed hydroalkylation method is reported for the synthesis of structurally diverse beta-chiral amides from readily accessible beta-alkyl-alpha,beta-unsaturated amides. The regio-reversed hydronickellation process provides a complementary approach to access enantioenriched beta-functionalization amides with a stereocenter at the beta-position.
Article
Chemistry, Organic
Ruiqi Tong, Song Liu, Chen Zhao, Dongyang Jiang, Lu Gao, Wanshu Wang, Bengui Ye, Zhenlei Song
Summary: A new nonracemic reagent has been developed for the asymmetric crotylboration of aldehydes. This reaction provides compounds with high yields and excellent stereo-selectivity, showcasing its potential in the synthesis of polyketide natural products.
Article
Chemistry, Multidisciplinary
Shang Gao, Jiaming Liu, Ming Chen
Summary: The study successfully synthesized compounds with high optical purity through catalytic asymmetric reactions, including (Z)-delta-hydroxymethyl-anti-homoallylic alcohols and alpha,beta-unsaturated aldehydes. Enantioconvergent pathways were utilized to achieve excellent optical purity.
Article
Chemistry, Organic
Toshimichi Kobayashi, Soshi Nishino, Masahiro Miura, Koji Hirano
Summary: A copper-catalyzed silylamination reaction has been developed for the synthesis of β-silyl-α-amino acid derivatives, which are of great interest in medicinal and pharmaceutical chemistry. The use of a suitable chiral ligand enables asymmetric induction, leading to the formation of optically active compounds with high enantiomeric ratios.
Article
Chemistry, Physical
Lin Liu, Yanhong Liu, Yiying Yang, Chengbu Liu, Dongju Zhang
Summary: This study presents a DFT-based comparative mechanistic study on the Cu/Pd-cocatalyzed four-component borocarbonylative reactions. The experimental observation that aryl iodides deliver beta-boryl ketones while aryl triflates afford beta-boryl vinyl esters is rationalized. The divergence in reactivity is attributed to the different formation rates of intermediates in the copper and palladium catalytic cycles.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Organic
Qing-Chun Zhang, Zuo-Lin Lu, Chen Hu, Kejie Zhu, Meifen Jiang, Zedu Huang, Fener Chen
Summary: The study introduces an efficient, stereoselective method for synthesizing chiral aryl beta-hydroxy alpha-amino acids and their derivatives. The method, based on ketoreductase (KRED)-catalyzed dynamic reductive kinetic resolution (DYRKR) of aryl alpha-amino beta-keto esters, shows promising results in terms of yield, diastereoselectivity, and enantioselectivity, demonstrating potential for practical synthesis applications such as the chemo-enzymatic total synthesis of thiamphenicol.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Akihiro Koga, Maki Matsuda, Rin Tanaka, Minami Endo, Yasunori Yamada, Takeshi Hanamoto
Summary: In this study, various nitrogen nucleophiles were easily added to in situ-generated 1-(trifluoromethyl)-2-(phenylthio)ethyne to afford the corresponding trifluoromethyl enamines in good-to-high yields and with high regio- and stereocontrol under very mild conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Gao Shang, Duan Meng, Kendall N. Houk, Chen Ming
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Inorganic & Nuclear
Jacob T. Mayhugh, Julie E. Niklas, Madeleine G. Forbes, John D. Gorden, Anne E. Gorden
INORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Shang Gao, Meng Duan, Qianzhen Shao, K. N. Houk, Ming Chen
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Shang Gao, Meng Duan, Jiaming Liu, Peiyuan Yu, Kendall N. Houk, Ming Chen
Summary: This study presents the development of stereodivergent syntheses of enantioenriched homoallylic alcohols using a chiral nonracemic alpha-CH(2)Bpin-substituted crotylboronate. The catalyst-controlled stereoselectivity allowed for the synthesis of complementary stereoisomers of chiral homoallylic alcohols from the same boron reagent. Computational studies were conducted to investigate the origins of the observed stereoselectivity, and the resulting products are valuable for the rapid construction of polyketide structural frameworks.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
J. E. Niklas, E. A. Hiti, G. R. Wilkinson, J. T. Mayhugh, J. D. Gorden, A. E. Gorden
Summary: Regioisomerism of a phenyl spacer affects the number of nuclei involved in self-assembly with pyrrole/schiff base ditopic ligands. The bulky benzyl ester substituents promote the formation of di-and tetranuclear complexes. The resulting unusual tetranuclear zinc molecular square is characterized, and the formation of helicates versus mesocates is discussed.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Organic
Julie A. Wilson, Zi Jie Lin, Isabelle Rodriguez, Thong Ta, Luke Martz, Dominic Fico, Shanina S. Johnson, John D. Gorden, Kerri L. Shelton, Lauren B. King
Summary: A series of N,N'-bis-substituted triazolium salts were synthesized and tested for their antimicrobial activities against a panel of representative ESKAPE pathogens. Compounds 7 and 12 exhibited significant antimicrobial activities against all pathogens, including a vancomycin-resistant strain of Enterococcus faecium and a multidrug resistant strain of Acinetobacter baumannii. The structure activity relationship of N,N'-bis-substituted triazolium salts suggests a potential selectivity of gram-positive or gram-negative bacteria based on the heterocycle center, highlighting their potent antimicrobial properties against multiple ESKAPE bacterial pathogens.
JOURNAL OF HETEROCYCLIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jiaming Liu, Shang Gao, Ming Chen
Summary: The study describes the development of a new alpha-borylmethyl-(Z)-crotylboronate reagent and its successful application in highly stereo- and enantioselective syntheses of (E)-delta-hydroxymethyl-syn-homoallylic alcohols. Starting from 1,4-pentadiene, the reagent was synthesized in two steps with high Z-selectivity and enantioselectivity, leading to the formation of highly enantioenriched products upon subsequent aldehyde allylboration.
Article
Chemistry, Organic
Jiaming Liu, Shang Gao, Ming Chen
Summary: Highly stereo- and enantioselective synthesis of (E)-delta-hydroxymethyl-anti-homoallylic alcohols is achieved through reactions between aldehydes and chiral nonracemic alpha-borylmethyl-(E)-crotylboronate, resulting in high E-selectivities and enantioselectivities.
Article
Chemistry, Multidisciplinary
Shang Gao, Meng Duan, Laura R. Andreola, Peiyuan Yu, Steven E. Wheeler, Kendall N. Houk, Ming Chen
Summary: We report a rare example of enantiodivergent aldehyde addition with beta-alkenyl allylic boronates via chiral Bronsted acid catalysis. The use of 2,6-di-9-anthracenyl-substituted chiral phosphoric acid catalyst enabled the asymmetric allylation using beta-vinyl substituted allylic boronate, leading to alcohols with R absolute configuration. Surprisingly, the sense of asymmetric induction of the catalyst in these reactions was opposite to previous reports. Moreover, the reactions with beta-2-propenyl substituted allylic boronate under the same acid catalyst resulted in the formation of homoallylic alcohol products with S absolute configuration. Computational studies suggested that unusual substrate-catalyst C-H...pi interactions in the favored reaction transition state were responsible for the observed enantiodivergence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jie Zhu, Menghua Xu, Baihui Gong, Aijun Lin, Shang Gao
Summary: Here, we report a tandem reaction of para-quinone methides with TMSCF2Br to synthesize bromofluoroalkenes in a Z-selective manner. TMSCF2Br, known as a difluorocarbene precursor, exhibits an alternative role as a formal bromofluorocarbene surrogate in this transformation. The resulting alkenyl bromide unit can undergo various transformations.
Article
Chemistry, Inorganic & Nuclear
Dylan M. T. Eralie, Tessa M. Hoang, Justin A. Williamson, Daniel K. Unruh, John D. Gorden, Anne E. V. Gorden
Summary: In this work, five cerium-(IV) complexes were synthesized, three of which were structural isomorphs from the same pyrasal ligand. The solid-state result was identified through structural analysis, which depended on the initial pH of the reaction solution and the temperature. The pyrasal ligands used in this study have weaker binding due to the electron-withdrawing effect of the nitrogen atoms within the pyrazine ring. The electron-withdrawing effect also deactivates the second amine after the first condensation with salicylaldehyde. Even with extended reaction times and excess ligand, without a metal template, only one salicylaldehyde is added.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Jinchun Qiu, Curt N. Bateman, Shuai Lu, Gary C. George III, Xiaopeng Li, John D. Gorden, Serhii Vasylevskyi, Anthony F. Cozzolino
Summary: A water-stable bidentate pnictogen bond donor has been found to have high binding affinities for cyanide, cyanate, and acetate. This opens up possibilities for anion recognition and noncovalent catalysis using this pnictogen bond donor motif. The binding behavior of the pnictogen bond donor was studied, and the high binding constants were confirmed through calculations.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shang Gao, Jiaming Liu, Ming Chen
Summary: The study successfully synthesized compounds with high optical purity through catalytic asymmetric reactions, including (Z)-delta-hydroxymethyl-anti-homoallylic alcohols and alpha,beta-unsaturated aldehydes. Enantioconvergent pathways were utilized to achieve excellent optical purity.
Article
Chemistry, Multidisciplinary
Jorge H. S. K. Monteiro, Ethan A. Hiti, Emily E. Hardy, Grant R. Wilkinson, John D. Gorden, Anne E. Gorden, Ana de Bettencourt-Dias
Summary: A new naphthylsalophen and its 3:2 ligand-to-lanthanide sandwich-type complexes were isolated, showing characteristic metal-centered emission for Nd-III, Er-III, and Yb-III when excited at 380 nm. Upon 980 nm excitation, Er-centered upconversion emission at 543 and 656 nm was observed in mixed lanthanide and the Er complexes, with low power densities as 2.18 W cm(-2).
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Timothy H. Barnes, Kara F. Johnson, John D. Gorden, Bradley L. Merner
CHEMICAL COMMUNICATIONS
(2020)
