Article
Chemistry, Applied
Min Liu, Jianning Liao, Yujie Dong, Wangyu Shi, Yimin Hu, Jiaqing Xu, Wei Wang, Yong Xu, Hongchao Guo
Summary: The acidic hydrogen-tethered allylic carbonates were successfully applied in phosphine catalysis, showing high yields in (4+2) annulation reactions with sulfamate-derived cyclic imines. A moderate ee was obtained, and the zwitterionic intermediate acted as a four-membered synthon.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Shabbir Ahmed Khan, A. Sanjeeva Kumar, K. C. Kumara Swamy
Summary: DBU-catalyzed spiro-annulation and ring expansion/dominoreaction of delta-acetoxy allenoates with cycl-2-ene-N-sulfonyl hydrazides led to ring-expanded products. On the other hand, cycl-3-ene/ane-N-sulfonyl hydrazones under similar conditions gave pyrazolecores. The key intermediates of spirocyclic and dienyl-amine were isolated and characterized. An extension to (R)-(-)-carvone-derived sulfonyl hydrazide also resulted in ring expansion and formation of pyrazoloazepine.
Article
Chemistry, Organic
Tingting Yan, Kaki Raveendra Babu, Yong Wu, Yang Li, Yuhai Tang, Silong Xu
Summary: A phosphine-catalyzed olefinic cross-coupling reaction between benzyl halides and fumarates has been described, providing trisubstituted alkenes with good yields and excellent E-selectivity under metal-free conditions. Mechanistic studies suggest a catalytic cycle involving phosphorus ylide formation, Michael addition, water-assisted hydrogen transfer, and phosphine elimination.
Article
Chemistry, Multidisciplinary
Wen-Xuan Lin, Zhuolin Pei, Cunxi Gong, Huilin Mo, Kai Yang, Ling-Bo Qu, Donghui Wei, Jin-Shuai Song, Shi-Jun Li, Yu Lan
Summary: In the study of the mechanism of phosphine-catalyzed [8+2] cycloaddition, it was found that electrophilicity plays a role in hindering nucleophilic attack but is not predictive of priority.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Fuhao Zhang, Xuan Dai, Lei Dai, Wenrui Zheng, Wai-Lun Chan, Xiaodong Tang, Xumu Zhang, Yixin Lu
Summary: A phosphine-catalyzed highly enantioselective and diastereoselective (3+2) annulation reaction has been developed, allowing convenient access to a range of highly functionalized chiral pyrrolidines. This method utilizes vinylcyclopropanes as a synthon for phosphine-mediated asymmetric annulation, offering new opportunities for the application of cyclopropanes substrates in phosphine-catalyzed organic transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Applied
Yi-Chao Li, Yu-Hao Wang, Subarna Jyoti Kalita, Yi-Yong Huang
Summary: This review summarizes the recent advancements in nucleophilic phosphine catalysis for incorporating fluorine/s or fluoroalkyl group/s into organic molecules, focusing on the methodological progress of cycloaddition, addition, and coupling reactions using fluorinated building blocks as electrophilic and/or nucleophilic partners. The article highlights the synthetic strategies, proposed reaction mechanisms, and synthetic utilities of these organofluorine compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Chuan Xiang Alvin Tan, Rui Li, Fuhao Zhang, Lei Dai, Nisar Ullah, Yixin Lu
Summary: A sequential phosphine-catalyzed asymmetric [3+2] annulation of aldimines has been developed, utilizing an oxidative central-to-axial chirality transfer strategy. This approach is operationally simple and allows for the rapid synthesis of highly enantioselective 2-arylpyrroles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Santigopal Mondal, Arghya Ghosh, Akkattu T. Biju
Summary: This article highlights the recent advances in the N-heterocyclic carbene (NHC)-organocatalyzed generation of azolium enolate intermediates and their subsequent interception with electrophiles. The NHC-bound azolium intermediates are generated by adding NHCs to suitably substituted aldehydes, acid derivatives, or ketenes. A wide range of coupling partners can intercept the azolium enolates to form [2+n] cycloadducts (n=2,3,4) and various alpha-functionalized compounds. Enantioselective synthesis of the target compounds is achieved with chiral NHCs.
Article
Chemistry, Applied
Jianning Liao, Qihuan Han, Min Liu, Wangyu Shi, Jiaqing Xu, Wei Wang, Yongjun Wu, Hongchao Guo
Summary: Phosphine-catalyzed annulation of acidic hydrogen-tethered allylic carbonates with electron-deficient alkenes was achieved, providing various polysubstituted spirocyclohexenes, spirocyclohexanones or cyclohexanones in moderate to high yields under mild reaction conditions. The reactions were successfully scaled up and the products were further transformed. The acidic hydrogen-tethered allylic carbonates exhibited good reactivity and potential for broader applications.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Juan Zhang, Wei Hao, Ying Chen, Zhen Wang, Jinzhong Yao, Weijun Yao
Summary: We have revealed a Rauhut-Currier reaction of γ-alkyl-substituted allenoate catalyzed by l-valine-derived amide phosphine to generate trisubstituted allenoate, which then undergoes a Diels-Alder reaction with maleimide or DMAD. The reaction achieves the construction of exo-bicyclic succinimide derivatives with three consecutive stereocenters and an exo-carbon-carbon double bond in high stereospecificity and almost quantitative yields.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Ting Wang, Yong You, Zhen-Hua Wang, Jian-Qiang Zhao, Yan-Ping Zhang, Jun-Qing Yin, Ming-Qiang Zhou, Bao-Dong Cui, Wei-Cheng Yuan
Summary: A copper-catalyzed decar-boxylative [3 + 2] cyclization reaction between alkyne-substituted cyclic carbamates and azlactones has been developed, providing optically pure gamma-butyrolactams bearing two adjacent tetrasubstituted carbon stereocenters in high yields with excellent stereo-selectivities (up to 99% yield, 99:1 dr, and 99% ee). This represents the first successful asymmetric synthesis of gamma-butyrolactams containing sterically congested adjacent tetrasubstituted stereocenters via a decarboxylative cyclization pathway.
Article
Chemistry, Organic
Ke Li, Zhenjie Gan, Er-Qing Li, Zheng Duan
Summary: A novel phosphine-catalyzed (4 + 2) cyclization reaction has been reported for the generation of functionalized dihydropyran skeletons from electron-deficient conjugated dienes and enones. Mechanistic investigation reveals the formation of a new phosphonium zwitterion, which undergoes consecutive reactions. An asymmetric variant has also been developed through efficient and economical chiral phosphine catalysis.
Article
Chemistry, Multidisciplinary
Juan Zhang, Wei Hao, Ying Chen, Zhen Wang, Jinzhong Yao, Weijun Yao
Summary: We have disclosed a method for the construction of exo-bicyclic succinimide derivatives through the Rauhut-Currier reaction and Diels-Alder reaction, exhibiting high stereospecificity and close to quantitative yields.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Hui Chen, Mo Yang, Guoqiang Wang, Liuzhou Gao, Zhigang Ni, Jingxiang Zou, Shuhua Li
Summary: A borane-catalyzed sequential addition of terminal alkynes to para-substituted phenols has been developed, yielding ortho-propargylic alkylated phenols with congested quaternary carbons. Control experiments and DFT calculations suggest a sequential phenol alkenylation/hydroalkynylation process. The extension of this strategy to the construction of triaryl-substituted quaternary carbons demonstrates the broad utility of this method.
Article
Chemistry, Organic
Dongqiu Li, Fang Cheng, Yuhai Tang, Jing Li, Yang Li, Jiao Jiao, Silong Xu
Summary: The method described involves a phosphine-catalyzed internal redox [4 + 2] annulation of 1,4-enynoates with electron-deficient alkenes, resulting in the efficient synthesis of highly functionalized cyclohexenes with exclusive regioselectivity and high diastereoselectivity under mild conditions.
