Article
Chemistry, Applied
Romeric Galea, Gaelle Blond
Summary: In this study, [7,5]-fused bicyclic acetals, also known as furooxepines, were synthesized through a gold(I)-catalyzed domino reaction. This one-step reaction allows the formation of multiple bonds, heterocycles, and a tetrasubstituted carbon stereocenter with 100% atom economy.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Ling Liao, Zhi-Peng Zhao, Bo-Ning Gu, Jin-Sheng Yu, Jian Zhou
Summary: Researchers have developed a branch-selective hydroalkylation method using palladium catalysis for the reaction between alkoxyallenes and monofluorinated nucleophiles. This allows the construction of valuable α-monofluoroalkylated allylic ethers. It is the first catalytic hydrofluoroalkylation of alkoxyallenes and demonstrates broad substrate scope and diversified product elaborations. The asymmetric variant of this method also showed the potential to obtain chiral fluorine-containing allylic ethers with up to 68% enantiomeric excess.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Malgorzata Z. Makos, Marek Freindorf, Yunwen Tao, Elfi Kraka
Summary: This study investigates the mechanism of [NHC]Au(I)-catalyzed hydroalkoxylation of allene, revealing that the catalyst facilitates the reaction through a two-step mechanism. Results show that the π-Au C=C interactions in the products are stronger than those in the reactants, contributing to the exothermic nature of the reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Souta Misawa, Asaki Miyairi, Yoshihiro Oonishi, Steven P. Nolan, Yoshihiro Sato
Summary: Polarized alkynes such as ynol ethers and ynamides undergo Au(I)-catalyzed hydroalkoxylation/Claisen rearrangement cascade reactions with allylic alcohols, proceeding under mild conditions with high regioselectivity. The resulting gamma,delta-unsaturated esters or amides are formed in an atom-economical manner using the [Au(IPr)NTf(2)] catalyst.
SYNTHESIS-STUTTGART
(2021)
Review
Chemistry, Multidisciplinary
Santosh K. Nanda, Rosy Mallik
Summary: This review highlights the recent development on the hydroalkoxylation of alkynes for the synthesis of oxygen-containing entities, which has gained attention from the synthetic community for its rapid access to useful synthetic intermediates.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Qinglong Zhang, Weiwei Zi
Summary: The study presents a dual-metal catalyzed diastereodivergent coupling method for the synthesis of beta-amino alcohols with multiple stereoisomers, enabling the concise preparation of natural products such as mycestericins F and G.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Lingli Han, Kang Lv, Teng Wang, Zitong Meng, Jing Zhang, Tao Liu
Summary: Density functional theory (DFT) calculations were used to study the role of a pyridyl group in controlling the selectivity of palladium/Bri nsted acid-catalyzed methoxycarbonylation and hydromethoxylation reactions. The presence of the pyridyl group facilitated the methanolysis steps in both reactions, leading to the formation of linear ester methyl 3,4-dimethylpentanoate (P1) and hydromethoxylation product 2-methoxy-2,3-dimethylbutane (P2). On the other hand, the absence of the pyridyl group resulted in the inability to generate linear or branched methoxycarbonylation products, and the difficulty in hydromethoxylation without the assistance of the pyridyl group.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hafiz Saqib Ali, Aqeel A. A. Hussein, Mohammed Obies
Summary: In this study, the density functional theory (DFT) was used to investigate the Au(I)-catalyzed cyclization of propargylic amides. The results showed that different counteranions have a significant effect on the energy barriers of the reaction. Specifically, SbF6-, NTf2-, and ClO4- slowed down the deauration step in the 6-endo-dig pathway. It is suggested that the efficiency of the catalytic system can be improved by engineering the structure of the counteranions and the reaction medium.
Article
Chemistry, Organic
Jun-Sheng Wei, Song Yang, Yin Wei, Sima Shamsaddinimotlagh, Hossein Tavakol, Min Shi
Summary: A gold(i)-catalyzed intramolecular cyclization reaction was developed to synthesize functionalized morpholines, piperazines, and oxazepanes. The reaction proceeds via a carbene or non-carbene process and exhibits a broad substrate scope, good functional group tolerance, and mild reaction conditions. The reaction pathway can be modulated by the steric bulkiness or chain length of the substrate.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Zhuo-Wei Xu, Shaozhong Wang
Summary: Enantiomerically pure acyclic O,O-acetal compounds (up to 97% ee) have been synthesized through chemo-, regio- and enantioselective palladium-catalyzed addition of oximes to alkoxyallenes. DFT calculations support the favorable protonative hydropalladation pathway, in which the hydrogen bonding interaction between the amide group of the diphosphine ligand and the alkoxyallene is critical for the highly stereoselective formation of the dioxygenated stereogenic center.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Felipe de la Cruz-Martinez, Marc Martinez de Sarasa Buchaca, Juan Fernandez-Baeza, Luis F. Sanchez-Barba, Ana M. Rodriguez, Jose A. Castro-Osma, Agustin Lara-Sanchez
Summary: Despite the widespread interest in zinc catalysis for hydroelementation reactions, the use of zinc complexes as catalysts for the hydroalkoxylation of alkynyl alcohols has not been reported. However, scorpionate zinc complexes have been successfully designed as precatalysts for this reaction. Studies have shown the excellent selectivity of zinc amide complex 8 in promoting the intramolecular hydroalkoxylation process to yield exocyclic enol ethers under mild conditions.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ming Xiang, Dana E. Pfaffinger, Eliezer Ortiz, Gilmar A. Brito, Michael J. Krische
Summary: The first catalytic enantioselective ruthenium-catalyzed carbonyl reductive couplings of allene pronucleophiles have been described, leading to the formation of enantiomerically enriched diols. Internal chelation directs the intervention of (Z)-sigma-alkoxyallyl-ruthenium isomers, enabling stereospecific carbonyl addition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Chaosheng Luo, Juan V. Alegre-Requena, Stephen J. Sujansky, Spencer P. Pajk, Liliana C. Gallegos, Robert S. Paton, Jeffrey S. Bandar
Summary: This study investigates the mechanism of nucleophilic addition of alcohols to simple alkenes, revealing the influence of alcohol stoichiometry on reaction rate and proposing a new solution. The improved method does not require excess alcohol, expands the substrate scope, and utilizes more practical catalyst systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Robert J. Harris, Kohki Nakafuku, Robert G. Carden, Jacob C. Timmerman, Ross A. Widenhoefer
Summary: The mechanism of hydroamination of enantiomerically enriched, axially chiral (R)-1-aryl-1,2-butadienes with aniline catalyzed by (IPr)AuOTf involves the formation of a gold-x-allene intermediate, leading to the formation of racemic product rac-2, where approximately 30% of rac-2 is formed directly from (R)-1 without the intermediacy of rac-1.
Article
Chemistry, Multidisciplinary
Yoshihiko Yamamoto, Tomoya Takase, Eisuke Kuroyanagi, Takeshi Yasui
Summary: In this study, a new class of difluoromethylated diarylmethanes was synthesized through Fe(OTf)(3)-catalyzed reaction, demonstrating the relationship between substrate structure and catalyst behavior.
CHEMICAL COMMUNICATIONS
(2021)