Article
Chemistry, Organic
Chuan-Ming Hong, Si-Qi Xiong, Xue Zhang, Kai-Xian Ma, Qing-Hua Li, Tang-Lin Liu
Summary: This paper discloses a silver-catalyzed 1,3-aza-benzyl migration of allyl alcohols by utilizing chelation-assisted selective cleavage of an unstrained C(sp3)-C(sp3) bond. This approach provides an available, efficient, high atom-economic, and environmentally benign procedure, leading to alkylation products with broad substrate scopes and excellent yields. The migration proceeds via a one-pot, two-step process involving a free-state alkyl metal species.
Article
Chemistry, Multidisciplinary
Suzuka Shibata, Koutarou Amano, Tatsuhiro Kojima, Keiji Mori
Summary: A Lewis acid-catalyzed 1,3-aminomethyl migration reaction was studied. Treatment of δ-amino acid derivatives with a catalytic amount of Sc(OTf)(3) resulted in smooth migration of the aminomethyl group, leading to the formation of & beta;-amino acid derivatives in moderate to good yields. Detailed investigation revealed that the migration reaction proceeded via a fragmentation/recombination pathway.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Guillermo Canudo-Barreras, Daniel Salvador, Raquel P. Herrera, M. Concepcion Gimeno
Summary: This work demonstrates the gold-catalyzed formation of 1,3-thiazine/1,3-thiazinane and the isolation of these tautomers. The developed protocol allows for the efficient synthesis of various 1,3-thiazine derivatives and the generation of different isomers depending on the compound's state. This study has implications for the synthesis of biologically relevant molecules and the understanding of tautomerism.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Melisa Alkan, Haley K. K. Banovetz, Mark S. S. Gordon, Levi M. M. Stanley
Summary: A combination of density functional theory (DFT), second order perturbation theory (MP2) calculations, and experimental methods were used to investigate the computational and mechanistic studies of Pd-catalyzed alkene carboacylation via ester bond activation. The key elementary steps of the catalytic cycle were examined, revealing a novel mechanism for the carboacylation reaction. The calculations showed that the Pd(II) intermediate preceding migratory insertion is a cationic intermediate, and a new organoboron species was identified as a nucleophile in this transition metal-catalyzed reaction. Experimental control studies confirmed the computational findings.
Article
Chemistry, Multidisciplinary
Sebastian Peil, Alejandro Gutierrez Gonzalez, Markus Leutzsch, Alois Fuerstner
Summary: This study demonstrates the highly unorthodox hydrogenation transformation of an internal alkyne using [Cp*RuCl](4) as a precatalyst. The reaction shows regioselectivity and forms vinyl carbene complexes with various binding modes as intermediates. The access to spirocyclic and bridged ring systems through this reaction is of great significance in medicinal chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Krishna Kanta Das, Asim Kumar Ghosh, Tamanna Mallick, Naznin Ara Begum, Alakananda Hajra
Summary: A Cu(I)-catalyzed 1,3-oxo alkylation reaction was developed to construct N-1-alkylated indazolone derivatives. This cascade reaction involves the sequential functionalization of N1 and C3 positions of indazole, forming C-N and C-O bonds with yields of 41-89%. The synthesized compounds showed efficient quantum yields and high Stoke shift values, indicating a possible aerobic manifold through single electron transfer.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Jianjun Liu, Shengli Zuo, Jieying Huang, Fan Zhang, Ang Zuo
Summary: This study reports for the first time the synthesis of 1,3-substituted-1,3-dihydro-benzimidazolones using photoinduced copper catalysis. The results demonstrate the great potential of this method for practical and green synthesis schemes.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Oksana Bilyk, Gabriel S. Oliveira, Rafaela M. de Angelo, Michell O. Almeida, Kathia Maria Honorio, Finian J. Leeper, Marcio V. B. Dias, Peter F. Leadlay
Summary: The stereospecific formation of a spiroacetal is a key step in the biosynthesis of various polyketides. This study reveals the involvement of a novel spiroacetal cyclase in the biosynthesis of ossamycin and oligomycin. The deletion of the corresponding gene abolishes oligomycin production and leads to the production of oligomycin-like metabolites lacking the spiroacetal structure.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Mu-Jia Luo, Gui-Fen Lv, Jing-Hao Qin, Chong-Hui Xu, Yang Li, Jin-Heng Li
Summary: This study presents a rhodium-catalyzed electrochemical reaction for the selective synthesis of structurally diverse hexasubstituted arenes. The method demonstrates excellent selectivity and high atom economy.
Article
Chemistry, Multidisciplinary
Mu-Jia Luo, Gui-Fen Lv, Jing-Hao Qin, Chong-Hui Xu, Yang Li, Jin-Heng Li
Summary: A cooperative rhodium-catalyzed electrochemical 1,3-butadiyne [2 + 2 + 2] cyclotrimerization is presented, which selectively produces hexasubstituted arenes. The method features high selectivity, good functional group tolerance, and high atom economy.
Article
Chemistry, Multidisciplinary
Liangliang Qi, Qiu-Quan Pan, Xiao-Xue Wei, Xiaobo Pang, Zitong Liu, Xing-Zhong Shu
Summary: Transition-metal-catalyzed sila-cycloaddition has been limited to specific sila-synthons, but this study demonstrates the potential of reductive nickel catalysis for using chlorosilanes as industrial feedstock chemicals. The reaction extends reductive coupling from carbocycle to silacarbocycle synthesis and from C-Si bond formation to sila-cycloaddition reactions. It offers a mild and versatile approach to access silacyclopent-3-enes and spirosilacarbocycles, with demonstrated optical properties and structural variations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ming Chen, Guangbin Dong
Summary: This article describes a platinum-catalyzed desaturation of cyclic ketones to their conjugated alpha,beta-unsaturated counterparts, which operates under mild conditions without the need for strong bases or acids. The method shows good functional group tolerance and can be applied to diverse and complex structures. The mechanism involves fast and reversible alpha-deprotonation followed by a rate-determining beta-hydrogen elimination process, distinguishing it from prior palladium-catalyzed methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Mizuki Yamazaki, Tomoyuki Yoshimura, Jun-ichi Matsuo
Summary: 1,3-Cyclobutanediones reacted with aromatic aldehydes to produce cyclic beta-keto esters, catalyzed by a small amount of potassium ethoxide. The effects of alkoxide catalysts and spiro cyclic groups on the 1,3-cyclobutanediones were examined.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Organic
Shuai Liu, Lu Zhang, Liang Xu, Pin Gao, Xin-Hua Duan, Li-Na Guo
Summary: This study describes a concise Fe-catalyzed alkylazidation of alpha-trifluormethylalkenes via a C-C bond cleavage/radical addition/azidation cascade. The protocol offers a practical and step-economic approach to the synthesis of tertiary alpha-trifluoromethyl azides, with broad substrate scope, excellent functional group compatibility, and the ability to be performed on a gram scale.
Article
Chemistry, Physical
Adam Cook, Haydn MacLean, Piers St Onge, Stephen G. Newman
Summary: A catalytic method for direct deoxygenation of various C-O bond-containing functional groups is reported. The reaction, using a Ni(II) pre-catalyst and silane reducing agent, selectively reduces alcohols, epoxides, ethers, aldehydes, and ketones to their corresponding alkanes while leaving other functional groups untouched. Practical applications in catalytic deuteration, benzyl ether deprotection, and valorization of biomass-derived feedstocks demonstrate the versatility of this methodology.
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
