Article
Multidisciplinary Sciences
Xiao-Xu Wang, Yuan-Tai Xu, Zhi-Lin Zhang, Xi Lu, Yao Fu
Summary: The authors report a nickel-catalysed hydroalkylation of unactivated alkenes to obtain branched alkyl carboxylic acids or alkyl amines. The reaction shows excellent regioselectivity and allows for site-selective late-stage functionalization of biorelevant molecules. The success of the reaction relies on the use of suitable directing groups and the investigation of ligand effects and reaction mechanisms.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Marie-Claire Giel, Andrew S. Barrow, Christopher J. Smedley, William Lewis, John E. Moses
Summary: This study presents a novel and mild method for catalytic Markovnikov hydration of (E)-aryl enynes to corresponding enones using a bench-stable aminium salt, TBPA. The chemoselective and diastereoselective transformation proceeds under neutral metal-free conditions, delivering excellent product yields. The utility of this transformation is demonstrated through the synthesis of biologically important (E)-3-styrylisocoumarins, including a formal synthesis of achlisocoumarin III.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Tian-Hong Jing, Kai-Chun Zhao, Guang-Hui Shi, Yi-Ying Zhuang, Xiao-Chao Chen, Xiao-Li Zhao, Yong Lu, Ye Liu
Summary: A series of bis-P,O-hybrid ligands were synthesized and characterized. The crystal structures showed that the ligand of L2 acted as a typical trans-positioned diphosphine as observed in the complexes Pd(L2)(OAc)2 and Pd(L2)Cl2, but also potentially as a P,P,O-tripodal pincer. Under mild conditions, L2 enabled Pd(OAc)2 to exhibit remarkable performance in the alkoxycarbonylation of vinyl arenes with high activity and excellent regioselectivity.
JOURNAL OF CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Caiyou Chen, Gregory C. C. Fu
Summary: Carbon-oxygen bonds are common in organic molecules, making methods for their construction with control of stereoselectivity important. The widely used Williamson ether synthesis has limitations in terms of scope and stereochemistry due to its reaction mechanism. Transition-metal catalysis has the potential to overcome these limitations but progress has been limited, especially in controlling enantioselectivity. We demonstrate that a readily available copper catalyst can achieve enantioconvergent substitution reactions of α-haloamides with oxygen nucleophiles, offering a promising solution to the challenge of enantioselective alkylations of heteroatom nucleophiles.
Review
Chemistry, Inorganic & Nuclear
Salahudeen Shamna, Jaleel Fairoosa, C. M. A. Afsina, Gopinathan Anilkumar
Summary: Hydrosilylation is a significant reaction in silicon chemistry, which involves the addition of silicon hydrides across C-C multiple bonds. It is an efficient method for the formation of organosilicon compounds. This review summarizes the recent advances in Palladium-catalysed hydrosilylation reactions over the past twelve years from 2008 to 2020, aiming to improve the activity and selectivity of catalysts for the production of organosilicon materials.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Charlotte S. Richards-Taylor, Michael C. Willis
Summary: A synthetic route to benzosultams was reported, using palladium-catalysed aminsulfonylation of alkenyl iodides as the initial step, followed by an intramolecular transformation to form benzosultams. The method allows for good variation of starting alkenyl iodides and was shown to be more efficient than a related SNAr route.
Article
Chemistry, Multidisciplinary
Yangbin Jin, Yaru Jing, Chunsheng Li, Meng Li, Wanqing Wu, Zhuofeng Ke, Huanfeng Jiang
Summary: A palladium-catalysed oxidative amination method has been developed for the synthesis of versatile and diverse allylamines, with high yields and good selectivity.
Editorial Material
Chemistry, Multidisciplinary
Hirokazu Tsukamoto, Kazuya Ito, Tatsuhiko Ueno, Mitsugu Shiraishi, Yoshinori Kondo, Takayuki Doi
Summary: Palladium(0)/monophosphine complexes catalyze anti-selective alkylative, arylative, and alkynylative cyclizations of alkynyl electrophiles with organometallic reagents. Triphenylphosphine (PPh3)-ligated palladium(0) catalyzes the cyclization of 5-alkynals to afford 2-cyclohexen-1-ol and 2-alkylidene-cyclopentanol derivatives. Palladium/tricyclohexylphosphine (PCy3) catalyst switches the regioselectivity in the cyclization of conjugated diyne-aldehydes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Hirokazu Tsukamoto, Kazuya Ito, Tatsuhiko Ueno, Mitsugu Shiraishi, Yoshinori Kondo, Takayuki Doi
Summary: Palladium(0)/monophosphine complexes catalyze anti-selective cyclizations of alkynyl electrophiles with organometallic reagents. The reaction proceeds via novel oxidative addition, transmetalation, and reductive elimination, resulting in the formation of cyclic products. The regioselectivity of the cyclization can be controlled by the choice of phosphine ligand.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Soshi Nishino, Yuji Nishii, Koji Hirano
Summary: A copper-catalyzed reaction has been developed for the regio- and diastereoselective borylamination of alpha,beta-unsaturated esters with B(2)pin(2) and hydroxylamines. The reaction delivers acyclic beta-boryl-alpha-amino acid derivatives with high anti-diastereoselectivity, which is difficult to achieve using established methods. Furthermore, the use of a chiral phosphoramidite ligand allows for the enantioselective synthesis of optically active beta-borylated alpha-amino acids. The resulting products can be further transformed into beta-functionalized alpha-amino acids, which are of great interest in medicinal chemistry.
Article
Chemistry, Multidisciplinary
Rui Liu, Meng-Lan Shen, Lian-Feng Fan, Xiao-Le Zhou, Pu-Sheng Wang, Liu-Zhu Gong
Summary: Allylamines are important for synthesizing bioactive compounds and can be obtained through the palladium-catalyzed allylic C-H amination of 1,4-dienes. This reaction favors the formation of thermodynamically unstable Z-allylamines with aromatic amines. Aliphatic cyclic amines can also participate, but linear dienyl allylic amines are the main products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Laszlo Kollar, Adam Erdelyi, Haroon Rasheed, Attila Takacs
Summary: The study presents a novel synthetic method for producing N-acylnortropane derivatives of biological importance by aminocarbonylation reactions using tropane-based amines as N-nucleophiles and Pd(OAc)(2)/2 PPh3 catalysts, with the bidentate Xantphos ligand required for specific compounds. The resulting carboxamides were isolated and fully characterized, demonstrating the potential of this approach for accessing diverse structures of biologically relevant compounds.
Article
Chemistry, Multidisciplinary
Diana J. Wang, Karina Targos, Zachary K. Wickens
Summary: Allylic amines are important synthetic targets for various biologically active compounds. A new electrochemical process was developed in this study to prepare aliphatic allylic amines by coupling secondary amines and unactivated alkenes. This method allows for the functionalization of feedstock gaseous alkenes and can be used to synthesize complex biologically active molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Tanuja Tewari, Rohit Kumar, Samir H. Chikkali
Summary: This study reports the use of an iron catalyst in carbonylation reactions to convert alkynes to alpha,beta-unsaturated esters. The reaction is operationally simple and allows the synthesis of various unsaturated esters.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Tanuja Tewari, Rohit Kumar, Samir H. Chikkali
Summary: An iron catalyst is reported for the hydroalkoxycarbonylation of alkynes in the presence of CO, affording α,β-unsaturated esters. The reaction is operationally simple and tolerates various functional groups, offering facile access to a range of compounds.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Multidisciplinary Sciences
Farhad Fathieh, Markus J. Kalmutzki, Eugene A. Kapustin, Peter J. Waller, Jingjing Yang, Omar M. Yaghi
Article
Chemistry, Multidisciplinary
Evan P. Vanable, Jennifer L. Kennemur, Leo A. Joyce, Rebecca T. Ruck, Danielle M. Schultz, Kami L. Hull
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Organic
Barry M. Trost, Anugula Nagaraju, Feijun Wang, Zhijun Zuo, Jiayi Xu, Kami L. Hull
Article
Chemistry, Multidisciplinary
Xiaotian Qi, Daniel G. Kohler, Kami L. Hull, Peng Liu
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Physical
Samuel N. Gockel, SangHyun Lee, Brittany L. Gay, Kami L. Hull
Summary: This study developed an oxidative carboamination protocol utilizing alkylboronic acids as carbon-centered radical precursors to efficiently produce a variety of functionalized amines, with a broad scope in vinylarenes, amines, and alkylboronic acids. Preliminary mechanistic studies revealed a single-electron oxidation of the alkylboronic acid to generate a carbon-centered radical intermediate that undergoes C-N bond formation across the olefin.
Article
Chemistry, Organic
Travis L. Buchanan, Samuel N. Gockel, Alexander M. Veatch, Ya-Nong Wang, Kami L. Hull
Summary: A general system for achieving three-component intermolecular carbofunctionalization of alkenes has been presented, including carboetherification, carboesterification, carboarylation, and carboamination. The scope of the reaction involves the carbon electrophile, the olefin, and the nucleophile. Additionally, the synthesis of gamma-lactams through a carboamination reaction was demonstrated in a telescoped three-step protocol.
Article
Chemistry, Multidisciplinary
Qi Yukki Li, Samuel N. Gockel, Grace A. Lutovsky, Kimberly S. DeGlopper, Neil J. Baldwin, Mark W. Bundesmann, Joseph W. Tucker, Scott W. Bagley, Tehshik P. Yoon
Summary: Reactions that allow for the formation of carbon-nitrogen, carbon-oxygen, and carbon-carbon bonds are crucial in synthetic chemistry. This study presents a copper-mediated, net-oxidative decarboxylative coupling reaction under visible-light irradiation, which enables the conversion of substrates without requiring harsh reaction conditions.
Article
Multidisciplinary Sciences
Zhao Wu, Samuel N. Gockel, Kami L. Hull
Summary: The use of photoredox catalysis allows for the hydroalkylation and hydroaminoalkylation of electronically diverse vinylarenes, providing a new approach for accessing valuable compounds with pharmacophores. The reaction's substrate scope was evaluated through numerous examples, demonstrating its synthetic utility and potential applications in organic synthesis.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Byung Joo Lee, Andrew R. Ickes, Anil K. Gupta, Seth C. Ensign, Tam D. Ho, Anika Tarasewicz, Evan P. Vanable, Gregory D. Kortman, Kami L. Hull
Summary: In this study, the rhodium-catalyzed hydroamination of allyl amine derivatives using various amine nucleophiles was presented. This methodology provides a powerful approach for the synthesis of unsymmetrical vicinal diamines and has been demonstrated to be useful in the rapid synthesis of bioactive molecules and analogs.
Article
Chemistry, Physical
An T. Ho, Seth C. Ensign, Evan P. Vanable, David Portillo, Jenna N. Humke, Gregory D. Kortman, Kami L. Hull
Summary: The Ir-catalyzed regioselective hydroamination of allyl amines and the catalyst-controlled regiodivergent hydroamination of homoallylic amines with aniline nucleophiles have been reported. These reactions can selectively synthesize diamines at different positions, and exhibit good reaction yields.
Article
Chemistry, Multidisciplinary
Brittany L. Gay, Ya-Nong Wang, Shreeja Bhatt, Anika Tarasewicz, Daniel J. Cooke, E. Grace Milem, Bufan Zhang, J. Brannon Gary, Michael L. Neidig, Kami L. Hull
Summary: In this study, the authors report a palladium/iron cocatalyzed aminoboration reaction that can successfully catalyze the aminoboration of simple alkenes. The iron cocatalyst plays a crucial role in releasing the transmetalation-active cationic alkylpalladium intermediate and acting as a redox shuttle in the regeneration of the Pd(II) catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Aja M. Nicely, Andrei G. Popov, Hannah C. Wendlandt, Grace L. Trammel, Daniel G. Kohler, Kami L. Hull
Summary: This study presents the copper-catalyzed three-componentcarboamination of atropates for the synthesis of α-aryl amino acid derivatives. The reaction scope is explored with respect to all three coupling partners: the alkyl halide, the atropate, and the aryl amine. A total of 41 examples are included, with yields of ≤92%. Both primary and secondary aryl amines participate in the carboamination along with α-haloesters, nitriles, and perfluoroiodoalkanes. Mechanistic investigations support a radical mechanism involving Cu-mediated C-N bond formation with the radical adduct.