Article
Chemistry, Multidisciplinary
Zhonglin Liu, Lucas J. Oxtoby, Juntao Sun, Zi-Qi Li, Nana Kim, Geraint H. M. Davies, Keary M. Engle
Summary: The site-selective palladium-catalyzed three-component coupling of unactivated alkenyl carbonyl compounds, aryl- or alkenylboronic acids, and N-fluorobenzenesulfonimide is described in this study. Regioselectivity is enhanced by tuning the steric environment on the bidentate directing auxiliary, facilitating challenging C(sp(3))-F reductive elimination from a Pd-IV intermediate to afford 1,2-carbofluorination products in moderate to good yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Ludmila A. Bulygina, Natalya S. Khrushcheva, Konstantin A. Lyssenko, Alexey A. Anisimov, Aleksander S. Peregudov
Summary: New organometallic derivatives were synthesized as ligand precursors and a 6-membered palladacycle was obtained through cyclopalladation. The structures of these compounds were characterized and a boat conformation of the 6-membered palladacycle was observed. The obtained bimetallic complex exhibited good catalytic activity in Suzuki reactions.
TRANSITION METAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jiao Zhou, Tenggang Jiao, Qiang Fu, Jun Wang, Ji Lu, Lin Yang, Jun Wei, Siping Wei, Xuefeng Cong, Na Hao
Summary: Selective C-H alkynylation of unprotected primary benzylamines and aliphatic aldehydes has been achieved using in situ-installed aldimine directing groups catalyzed by iridium. This method offers a straightforward synthesis of alkynylated primary benzylamine and aliphatic aldehyde derivatives with good substrate compatibility and high regioselectivity.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sharmila Pandey, Tanmoy Mandal, Sanajit Kumar Mandal
Summary: Three discrete Ru(II) complexes have been synthesized using different pyridine/pyrazine based tridentate ligands, with one bipyridine/phenanthroline and one chloride as co-ligands. The crystal structures of the complexes revealed monomeric structures. Density Functional Theory calculations showed different electronic properties and redox behavior for the complexes, depending on the ligands used. The catalytic behavior of the Ru-complexes was also influenced by the ligands, with different selectivity observed for oxidation reactions.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Katsuaki Kobayashi, Norihisa Fukaya, Hiroshi Nakazawa
Summary: The activation of a dibromo Co-terpyridine complex immobilized on a stationary phase (Co(tpy)Br-2@SiO2) as a hydrosilylation catalyst with K2CO3 as the activator was investigated. Good yields were obtained in the catalytic hydrosilylation reactions using Co(tpy)Br-2@SiO2 activated by K2CO3. Both the catalyst and activator were easily separable from the hydrosilylated product, allowing for a reusable hydrosilylation system. The Co(tpy)Br-2@SiO2/K2CO3 system was also found to be applicable in a continuous flow reactor as a catalyst in the stationary phase.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Applied
Agata Wawrzynczak, Sylwia Jarmolinska, Izabela Nowak
Summary: In this study, ordered nanostructured KIT-6 silica with different numbers of sulfonic groups were synthesized. The amount of the functional group precursor used affected the structural and textural parameters of the synthesized materials. The samples modified by grafting exhibited a stable mesoporous structure, while the ones synthesized by co-condensation showed characteristics of KIT-6 materials. The developed synthesis procedures yielded potential solid acid catalysts with desirable catalytic performances.
Article
Chemistry, Organic
Kyu Ree Lee, Subin Ahn, Sang-gi Lee
Summary: The study presents a novel method for the synthesis of monocyclic nine-membered N,O-heterocycles through a synergistic palladium/rhodium dual catalytic cycloaddition of vinylpropylene carbonates with N-sulfonyl-1,2,3-triazoles. Furthermore, the resulting oxazonines can be transformed into cis-fused [4.3.0] bicyclic compounds via a transannular Alder-ene rearrangement.
Article
Materials Science, Multidisciplinary
Rakesh Sen, Kousik Das, Subhrokoli Ghosh, Anand Dev Ranjan, Khokan Manna, Ayan Banerjee, Soumyajit Roy
Summary: We describe a light-driven interface engineering technique for a microcatalytic chip that enables facile para nitration with high selectivity. This technique has potential applications for the synthesis of aromatic compounds with high selectivity and atom economy.
MATERIALS ADVANCES
(2023)
Article
Materials Science, Multidisciplinary
Rakesh Sen, Kousik Das, Subhrokoli Ghosh, Anand Dev Ranjan, Khokan Manna, Ayan Banerjee, Soumyajit Roy
Summary: In this article, a light-driven interface engineering of a microcatalytic chip is reported, which enables high selective para nitration. By synthesizing pre-catalyst components and patterning them on a glass surface, the aromatic substrate anchoring and catalytic effects are optimized. This design can be used for the synthesis of aromatic hydrocarbons with high selectivity and atom economy.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Van T. Tran, Nana Kim, Camille Z. Rubel, Xiangyu Wu, Taeho Kang, Tanner C. Jankins, Zi-Qi Li, Matthew V. Joannou, Sloan Ayers, Milan Gembicky, Jake Bailey, Emily J. Sturgell, Brittany B. Sanchez, Jason S. Chen, Song Lin, Martin D. Eastgate, Steven R. Wisniewski, Keary M. Engle
Summary: A flurry of recent research has focused on utilizing nickel catalysis in organic synthesis. This report presents ten different bench-stable, 18-electron, formally zero-valent nickel-olefin complexes that serve as competent pre-catalysts in various reactions. Characterization and analysis shed light on the structure, bonding, and properties of these complexes, while their application in nickel-catalyzed reactions highlights the complementary nature of the different pre-catalysts within this toolkit.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ruihan Wang, Yidong Wang, Ruiqi Ding, Parker B. Staub, Christopher Z. Zhao, Peng Liu, Yi-Ming Wang
Summary: A newly-developed cationic cyclopentadienyliron dicarbonyl complex enables the conversion of propylene to its allylic C-C bond coupling products under catalytic conditions. This approach is also applicable to the allylic functionalization of simple alpha-olefins with distinctive branched selectivity. Experimental and computational studies reveal the allylic deprotonation of the metal-coordinated alkene as the turnover-limiting step and provide insights into the multifaceted roles of the newly designed ligand in promoting allylic C-H functionalization with enhanced reactivity and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Tobias Koengeter, Can Qin, Binh Khanh Mai, Qinghe Liu, Yucheng Mu, Peng Liu, Amir H. Hoveyda
Summary: This paper presents a stereoretentive strategy for catalytic cross-metathesis reaction between tri-, Z- or E-di, or monosubstituted olefins and Z- or E-2-bromo-2-butene, leading to the formation of various trisubstituted alkenyl bromides. The method is applicable for the generation of products containing polar moieties or sterically hindered alkenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Tao Zhang, Kangbao Zhong, Zhi-Keng Lin, Linbin Niu, Zi-Qi Li, Ruopeng Bai, Keary M. Engle, Yu Lan
Summary: In this study, computational evidence is presented to support the role of Zn coordination in accelerating reductive elimination from Ni(II) centers in Ni-catalyzed cross-couplings. The Zn-assisted pathway was found to have lower energy compared with direct reductive elimination from a Sigma-coordinated Ni(II) intermediate. Theoretical calculations reveal a significant Z-type Ni-Zn interaction that enhances reductive elimination.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Amit Kumar Simlandy, Turki M. Alturaifi, Johny M. Nguyen, Lucas J. Oxtoby, Quynh Nguyen Wong, Jason S. Chen, Peng Liu, Keary M. Engle
Summary: We report a transient directing group (TDG) strategy for site-selective palladium-catalyzed reductive Heck-type hydroalkenylation and hydroalkynylation of alkenylaldehydes using alkenyl and alkynyl bromides. This strategy allows for the construction of a stereocenter at the delta-position with respect to the aldehyde. Computational studies reveal the beneficial roles of rigid TDGs, such as L-tert-leucine, in promoting TDG binding and inducing high levels of enantioselectivity in alkene insertion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hui-Qi Ni, Malkanthi K. Karunananda, Tian Zeng, Shenghua Yang, Zhen Liu, K. N. Houk, Peng Liu, Keary M. Engle
Summary: Multistep organic synthesis allows the conversion of simple chemical feedstocks into more complex products with specific functions. This study introduces a novel approach to organic reactions that can generate multiple valuable products with different carbon skeletons in a single operation. Through a palladium-catalyzed reaction, a single alkene starting material can be converted into two structurally distinct products, demonstrating the potential for simultaneous access to diverse compounds. The findings of this study provide insights into the mechanistic details of this unique catalytic system and establish a new method for small-molecule library synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jingfeng Huo, Yue Fu, Melody J. Tang, Peng Liu, Guangbin Dong
Summary: In this research, the first nickel-catalyzed Catellani-type annulation of aryl triflates and chlorides was achieved to form various benzocyclobutene-fused norbornanes in high efficiency. Mechanistic studies revealed an unexpected outer-sphere concerted metalation/deprotonation pathway and the essential roles of the base and the triflate anion. Compared to palladium catalysis, the reaction showed a broad functional group tolerance and enhanced regioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Paul J. Chirik, Keary M. Engle, Eric M. Simmons, Steven R. Wisniewski
Summary: Earth-abundant metal (EAM) catalysis has significant impact on the sustainability and cost improvement in the pharmaceutical industry. It replaces precious metals like palladium and utilizes the reactivity of first-row metals to enable more efficient routes to clinical candidates. This article describes the strategy for building these capabilities within the process group, including the development of a reaction screening platform, scalability demonstration, and increasing mechanism understanding.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Review
Chemistry, Organic
Taeho Kang, Omar Apolinar, Keary M. Engle
Summary: In this Review, the various strategies, mechanisms, and catalysts that have been applied to achieve enantioinduction in alkene 1,2-DCF are discussed.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Multidisciplinary
Jicheng Wu, Peijing Jia, Rositha Kuniyil, Peng Liu, Weiping Tang
Summary: In this study, we report an efficient method for the stereoselective synthesis of challenging α-linked glycoconjugates using a Rh-II/chiral phosphoric acid (CPA)-cocatalyzed dynamic kinetic anomeric O-alkylation. By exploring various parameters of the cocatalytic system, we achieved excellent anomeric selectivity, excellent diastereoselectivity, broad substrate scope, and high efficiency for this glycosylation reaction. DFT calculations suggested that the anomeric selectivity was determined by steric interactions between the C2-carbon of the carbohydrate and the phenyl group of the metal carbenoid, while diastereoselectivity at the newly generated stereogenic center was influenced by π-π interactions with the C2-OBn substituent on the carbohydrate substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Liam S. S. Fitzgerald, Rachael L. L. McNulty, Andrew Greener, Miriam L. L. O'Duill
Summary: In this study, a programmable labeling platform is developed for the selective deuterium incorporation into indole compounds. C2-deuterated indoles are obtained using a reverse hydrogen isotope exchange strategy, which is the first non-directed C2-deuteration of indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Dennis A. Kutateladze, Binh Khanh Mai, Yuyang Dong, Yu Zhang, Peng Liu, Stephen L. Buchwald
Summary: A copper hydride-catalyzed approach has been developed for the synthesis of Z-configured trisubstituted alkenes with high stereo- and regioselectivity. This method provides a valuable strategy for accessing challenging classes of alkenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Lei Cheng, Dian Li, Binh Khanh Mai, Zhiyu Bo, Lida Cheng, Peng Liu, Yang Yang
Summary: The merger of photoredox catalysis and PLP biocatalysis enables the development of a new synthetic method for preparing valuable noncanonical amino acids, allowing controlled formation of chiral products.
Article
Chemistry, Organic
Yilin Cao, Zi-Qi Li, Keary M. Engle
Summary: A nickel-catalyzed heterocycle-directed 1,2-diarylation of alkenes with aryl iodide electrophiles and arylboronic acid neopentyl ester nucleophiles is reported, resulting in a series of 1,2,4-tri(hetero)aryl products under mild conditions. The transformation is enabled by a collection of azaheterocycle directing groups, giving moderate to excellent yields. The preparative utility of the method is demonstrated by a large-scale reaction.
TETRAHEDRON LETTERS
(2023)
