Article
Chemistry, Organic
Olfa Mhasni, Jalloul Bouajila, Farhat Rezgui
Summary: A highly α-regioselective N-nucleophilic allylic substitution reaction was conducted between cyclic MBH alcohols or acetates and imidazole or benzimidazole, using toluene as solvent and azeotropic distillation at reflux, resulting in good yields of N-substituted imidazole derivatives in the absence of catalysts or additives. On the other hand, the aza-Michael addition reaction of imidazole onto acyclic MBH alcohols was performed in refluxing toluene or methanol, with the presence of DABCO as an additive, leading to 1,4 adducts in yields of 70-84%.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xing Guo, Boming Shen, Chang Liu, Hongyue Zhao, Xuechen Li, Peiyuan Yu, Pengfei Li
Summary: Based on the frontier molecular orbital theory, two types of modified enones have been designed and successfully applied in the chiral phosphine-catalyzed stereoselective [1 + 4]-annulation of MBH carbonates. The reaction proceeds smoothly under mild conditions, exhibiting excellent functional group tolerance and providing a broad scope of enantioenriched 2,3-dihydrofurans with high efficiency. DFT calculations have been used to guide the design of additional enones and understand the origin of stereoselectivity. Furthermore, this method explores the application scope of enones and enriches the chemistry of [1 + 4]-annulations of MBH carbonates for the preparation of optically active multifunctional 2,3-dihydrofurans.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Biochemistry & Molecular Biology
Joel K. Annor-Gyamfi, Ebenezer Ametsetor, Kevin Meraz, Richard A. Bunce
Summary: An efficient synthetic route has been developed for the preparation of highly substituted dihydroquinolines and dihydronaphthyridines through a domino reaction of Morita-Baylis-Hillman acetates with primary aliphatic and aromatic amines. The reaction proceeds at 50-90 degrees C in DMF. The products were isolated in good to excellent yields, with dual reactivity observed in the annulations of MBH acetates incorporating a 2,5-difluorophenyl moiety.
Article
Chemistry, Organic
Naruhiro Gondo, Koki Fujimura, Ryuichi Hyakutake, Yoshihiro Ueda, Takeo Kawabata
Summary: Asymmetric regioselective vinylogous aza-Morita-Baylis-Hillman reactions were conducted using organocatalysis. The reactions between 3-vinylcyclopentenone and various aldimines, in the presence of chiral pyrrolidinopyridine catalysts, yielded 7-adducts with high regioselectivity and moderate enantioselectivity.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Zhen-Zhen Xie, Yu-Lun Qian, Yu Zheng, Qing-Lan Zhao, Jun-An Xiao, Hao-Yue Xiang, Kai Chen, Hua Yang
Summary: A new synthetic method has been developed for the efficient synthesis of chiral spirocyclic oxindole-alpha-methylene-gamma-lactams. The method utilizes Morita-Baylis-Hillman carbonates as substrates and quinidine derivatives as catalysts to achieve stereoselective control over the products. This research broadens the application of Morita-Baylis-Hillman carbonates in the asymmetric construction of spirocyclic oxindoles.
Article
Chemistry, Organic
Xiang-Hong He, Xue-Ju Fu, Gu Zhan, Nan Zhang, Xiang Li, Hong-Ping Zhu, Cheng Peng, Gu He, Bo Han
Summary: This study describes an organocatalytic asymmetric [3+3] annulation reaction using isatin-derived MBH carbonates and indolin-2-imines. The reaction provides a novel enantioselective approach for the synthesis of multifunctionalized alpha-carboline-spirooxindole hybrids with high yields and stereoselectivities. The synthesized compounds exhibit significant inhibition of proliferation in colorectal cancer cell lines, and the most potent compound activates autophagy and cytoprotective autophagy in HCT116 cells.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Lin Jiang, Liu-Dong Yu, Pei-Ying Peng, Hong-Li Li, Deng-Bang Jiang, Yi-Dan Wang, Ming-Long Yuan, Ming-Wei Yuan
Summary: A two-step metal-free process has been developed for the stereoselective allylic 1,3-dienylation of Morita-Baylis-Hillman (MBH) carbonates under mild reaction conditions. This transformation involves allylic alkylation with MBH carbonates followed by denitration, resulting in allylic 1,3-dienyl MBH derivatives with exclusive (E)-selectivity.
SYNTHETIC COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Shutao Wang, Yongliang Gao, Shaoli Song, Xinze Li, Zhuoqi Zhang, Jinbao Xiang, Lianyou Zheng
Summary: This article describes a Lewis base catalyzed allylation reaction between N-aryl amides and various Morita-Baylis-Hillman (MBH) carbonates. The substrate scope of MBH carbonates and amides is comprehensively explored, making this approach useful for the synthesis of diversified branched tertiary N-allylic amides, with broad substrate scope, mild reaction conditions, and scalability.
Article
Chemistry, Multidisciplinary
Lei Zhang, Wangzhen Bao, Yuchen Liang, Wenjing Pan, Dongyang Li, Lichun Kong, Zhi-Xiang Wang, Bo Peng
Summary: This study demonstrates the reversal of stereoselectivity in MBH-type [3,3]-rearrangement by using a new pair of rearrangement partners, leading to the synthesis of different types of alpha-aryl alpha,beta-unsaturated carbonyl derivatives. Mechanistic studies provide insights into the reaction pathway and the opposite stereoselectivities observed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Danna Chen, Yabo Deng, Shuo Sun, Pengfei Jia, Jinqi Huang, Wenjin Yan
Summary: This article introduces an asymmetric gamma-regioselective-alkylation reaction catalyzed by a chiral tertiary amine ((DHQ)(2)PHAL) which utilizes isatin-derived Morita-Baylis-Hillman carbonates and CF3-containing ketoimines. The reaction delivers chiral alpha-trifluoromethylamine derivatives and incorporates an oxindole motif with high yields, diastereoselectivities, and enantioselectivities. The subsequent deprotection reaction produces alpha-trifluoromethyl amines in a stereoselective manner. Furthermore, the product can be further derivatized to furnish fused polycyclic frameworks without compromising its stereoselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Prashant Shukla, Ambika Asati, Devkumari Patel, Manorama Singh, Vijai K. K. Rai, Ankita Rai
Summary: This study reports on the Morita Baylis-Hillman (MBH) reaction using various aldehydes with acrylonitrile and methyl acrylate as electron-deficient alkenes. A novel catalyst, EDC.HCl, is utilized in the presence of CuI to synthesize the MBH adduct. The synthetic protocol shows excellent product yield (up to 99%), ambient reaction conditions, shorter reaction time, and no side product formation.
Article
Chemistry, Physical
Ricardo Lucas Gomes Pimentel, Rodolfo B. da Silva, Mario Luiz Araujo de Almeida Vasconcellos, Claudio Gabriel Lima-Junior, Fausthon F. da Silva
Summary: This study explores the synthesis and characterization of a mixed-metal copper-manganese iminodiacetate 1D coordination polymer (Cu/Mn-IDA) and its application as a catalyst for the Morita-Baylis-Hillman reaction. The results demonstrate that under optimized conditions, the catalyst can achieve yields of up to 87% for various aldehyde substrates. Additionally, the catalyst exhibits good recyclability.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Organic
Jianning Liao, Jipan Dong, Jiaqing Xu, Wei Wang, Yongjun Wu, Yuxia Hou, Hongchao Guo
Summary: A phosphine-catalyzed [3 + 2] annulation reaction has been developed in this study to synthesize multifunctional isoxazoles with moderate to good yields and diastereoselectivities. The use of a spirocyclic chiral phosphine catalyst resulted in up to 89% ee.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Marta Papis, Raffaella Bucci, Alessandro Contini, Maria Luisa Gelmi, Leonardo Lo Presti, Giovanni Poli, Gianluigi Broggini, Camilla Loro
Summary: A phosphine-catalyzed domino assembly of six units of 2-bromomethyl acrylates was developed to synthesize polyalkenyl adducts containing two cyclohexenyl rings. This method involves initial dimerization and subsequent trimerization of the substrate, resulting in the formation of seven carbon-carbon bonds and four stereocenters. The protocol has also been successfully scaled up to gram-scale experiments.
Article
Chemistry, Organic
Atanu Mondal, Bishnupada Satpathi, S. S. Ramasastry
Summary: This study demonstrates a novel strategy for the phosphine-catalyzed intramolecular vinylogous aldol reaction of alpha-substituted enones, leading to the synthesis of various novel cyclic compounds and dibenzocycloheptanones with two contiguous stereocenters. The scope of this work is further expanded through transformations of the IVAR adducts, resulting in the synthesis of benzannulated nine-membered carbocyclic systems, interesting classes of dienes, trienes, and dienynes, as well as analogs of echinolactone D and russujaponol F.
