Article
Multidisciplinary Sciences
Lumin Zhang, Bethany M. DeMuynck, Alyson N. Paneque, Joy E. Rutherford, David A. Nagib
Summary: Carbenes, highly reactive intermediates, are successfully generated from common aldehydes via stable alpha-acyloxy halide intermediates, enabling diverse and valuable chemistry reactions. This strategy utilizes zinc carbenoids and earth-abundant metal salts as catalysts to achieve safe and selective carbene additions to sigma and pi bonds.
Article
Chemistry, Organic
Jie Zhang, Yaning Wang, Chang You, Mingying Shi, Xueling Mi, Sanzhong Luo
Summary: We report a synergetic chiral primary amine and rhodium catalysis for the asymmetric coupling of beta-ketocarbonyls and alkynes. This method enables the synthesis of linear allylation products with all-carbon quaternary centers in high regio- and enantioselectivities.
Article
Chemistry, Multidisciplinary
Jie Zhang, Xue Song, Zhi-Chao Chen, Wei Du, Ying-Chun Chen
Summary: A catalytic cyclopropanation reaction between benzyl bromides and activated alkenes has been developed using phosphonium ylide intermediates. The reaction produces densely functionalized cyclopropane derivatives with excellent diastereoselectivity, which can be further transformed into five-membered heterocycles. Moderate enantioselectivity can be achieved using a commercially available DuPhos catalyst.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Nuria Vazquez-Galinanes, Isabel Velo-Heleno, Martin Fananas-Mastral
Summary: A method for the use of vinyl epoxides in catalytic allylboration of alkynes is described, which allows for the synthesis of bifunctional skipped dienes bearing both an allylic alcohol and an alkenylboronate from simple starting materials with high regio- and stereoselectivity. These products show versatile reactivity and can be converted into cyclic boron compounds and polyenes.
Article
Chemistry, Organic
Mariliis Kimm, Ivar Jarving, Maksim Oseka, Tonis Kanger
Summary: Asymmetric rearrangement reactions are highlighted as a perfect tool for constructing new carbon-carbon bonds in an enantioselective manner. The article specifically discusses a new and straightforward procedure for synthesizing alpha-hydroxy ketones with high diastereo- and enantioselectivity through the enantioselective [2,3]-Wittig rearrangement of cinnamyloxycyclohexanone derivatives catalyzed by a commercially available primary amine.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Bo Zhou, Shuang Deng, Yin Xu, Xiaotian Qi, Guangbin Dong
Summary: This paper describes the development of a direct functionalization method for carbonyl beta C-H bonds without using directing groups. The reaction enables the beta-alkenylation of ketones with common alkynes through iridium catalysis, and it proceeds under redox neutral conditions, avoiding the need for strong acids or bases, and tolerates various functional groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Duhao Sun, Bing Zhou, Lanqin Liu, Xiaoyun Chen, Hong Hou, Ying Han, Chaoguo Yan, Yaocheng Shi, Shaoqun Zhu
Summary: This article presents a palladium-catalyzed method for the synthesis of borylated bicycles, fused cycles, and bridged cycles from terminal alkyne-derived enynes. The method demonstrated good isolated yields and was further utilized in large-scale reactions and synthetic derivatization of the borate group.
Article
Chemistry, Physical
Diego Olivieri, Riccardo Tarroni, Nicola Della Ca', Raffaella Mancuso, Bartolo Gabriele, Gilberto Spadoni, Carla Carfagna
Summary: We have developed a chemoselective method for the carbonylation of allylic substrates, leading to alkyl succinates with preservation of the X group. Our method exhibits a completely different selectivity compared to the classical substitutive carbonylation of allyl compounds. By optimizing the ligand and nucleophile, as well as through DFT calculations, we achieved moderate to good yields of succinate derivatives.
Article
Chemistry, Organic
Masahiro Sai
Summary: The isomerization of allylic alcohols is an important reaction, and this paper reports the development of an efficient catalytic system that allows for the isomerization of a broad range of substrates with high yields. The catalytic system was also successfully applied to a tandem reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Sijing Xue, Bart Limburg, Debasish Ghorai, Jordi Benet-Buchholz, Arjan W. Kleij
Summary: Dual palladium/photoredox-catalysis is an effective method for the decarboxylative asymmetric synthesis of vicinal alpha,beta-tri/tetra- or alpha,beta-tetrasubstituted homoallylic alcohols using Hantzsch-type esters as radical precursors. This methodology utilizes vinyl cyclic carbonates as accessible reagents to provide the target molecules in appreciable to good yields, high branch selectivity, and enantiomeric ratios of up to 94:6, making it a rare example of using prochiral electrophiles for the creation of vicinal congested carbon centers.
Article
Chemistry, Applied
Rikuo Hayashi, Kaori Ando, Taro Udagawa, Masahiro Sai
Summary: This study presents a method for synthesizing diverse beta-functionalized ketones from readily available 1-arylallylic alcohols in the presence of (trimethylsilyl)methylpotassium (TMSCH2K). The reaction proceeds via the formation of a highly nucleophilic dipotassio alpha,beta-dianion, which serves as a metal homoenolate equivalent and allows the one-pot synthesis of alpha,beta-difunctionalized ketones.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Gang Liu, Congcong Yin, Xuanliang Yang, Anqi Li, Minyan Wang, Xumu Zhang, Xiu-Qin Dong
Summary: A highly chemo- and enantioselective hydrogenation method for beta-sulfonyl-alpha,beta-unsaturated ketones was successfully developed, producing a variety of enantioenriched gamma-ketosulfones in good to high yields with excellent selectivities. Gram-scale asymmetric hydrogenation was carried out smoothly with high yields and selectivities. Preliminary DFT computations provided a reasonable explanation for the observed high chemoselectivity and enantioselectivity.
Article
Multidisciplinary Sciences
Long Li, Shan Wang, Pengfei Luo, Ran Wang, Zheng Wang, Xiaoguang Li, Yuhua Deng, Fangzhi Peng, Zhihui Shao
Summary: The authors developed a method to synthesize quaternary carbon spirocycles in one step from 1,3-enynes and pyrazolidine-type heterocycles via palladium catalysis, which is important for drug discovery and development. Their approach involves a chiral Pd-hydride-catalyzed cycloaddition to control stereoselectivity and suppress by-product formation. The synthesis tolerates a wide range of functional groups and allows for flexible incorporation of diverse cyclic nucleophiles.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Prashant Kumar, Pravesh Kumar, Sugumar Venkataramani, S. S. V. Ramasastry
Summary: This study reveals a new chemical reactivity pattern of allylic gem-diacetates and successfully synthesizes complex benzo[f]chromene compounds, demonstrating the versatility of the method. Additionally, interesting photochromic properties of the new classes of benzo[f]chromenes are discovered.
Article
Chemistry, Physical
Prashant Kumar, Pravesh Kumar, Sugumar Venkataramani, S. S. V. Ramasastry
Summary: This work explores the unusual chemical reactivity pattern of allylic gem-diacetates and establishes them as new prototypes for synthesizing complex benzo[f]chromene systems. The versatility of the method in synthesizing bioactive natural products based on chromene is demonstrated, along with the discovery of interesting photochromic properties of the new classes of benzo[f]chromenes.
Article
Chemistry, Organic
Peng Chen, Zhi-Yong Wang, Xiao-Shui Peng, Henry N. C. Wong
Summary: An efficient synthetic protocol involving iron-catalyzed cross-coupling of organolithium compounds with vinyl halides as key coupling partners is presented. Over 30 examples were obtained with moderate to good yields and high stereo-selectivities. The practicality of this method is evidenced by a gramscale synthesis, and a preliminary mechanistic investigation was also performed.
Article
Chemistry, Multidisciplinary
Shuai Huang, Gao-Peng Zhang, Yang-Jie Jiang, Fei-Le Yu, Chang-Hua Ding, Xue-Long Hou
Summary: This article presents a facile and efficient method for constructing vicinal tertiary and quaternary chiral carbon centers in synthetic chemistry. By using Kundig-type chiral N-heterocyclic carbene as the ligand, the reaction between Pd-catalyzed umpolung asymmetric allylic alkylation of hydrazones and monosubstituted allyl reagents achieves high yields and high selectivities.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Juan Wang, Yun-Fan Li, Juan Du, Shuai Huang, Chang-Hua Ding, Henry N. C. Wong, Xue-Long Hou
Summary: Alkynyl esters can undergo palladium-catalyzed asymmetric (3 + 2) cycloaddition with vinyl epoxides, leading to the formation of chiral dihydrofurans with high yields and high enantiomeric excess values when a chiral benzylic substituted P,N-ligand is used. The synthetic method has also been demonstrated for the synthesis of 2,3-cis-tetrahydrofuran.
Correction
Chemistry, Organic
Zhuliang Zhong, Mao-Yun Lyu, Hao-Ran Ma, Henry N. C. Wong, Xiao-Shui Peng
Summary: This review summarizes the most prominent applications of three pivotal reactions, enyne cycloisomerization, polyene cyclization, and quinone methide formation, in the total syntheses of natural products. The article provides an overview of the recent advancements in these reactions and offers a comprehensive review of relevant literature.
Review
Chemistry, Multidisciplinary
Lu-Qiong Huo, Xin-Hao Wang, Zhenguo Zhang, Zhenhua Jia, Xiao-Shui Peng, Henry N. C. Wong
Summary: This review summarizes the recent advances from 2012 to 2022 in the formation of carbon-carbon and carbon-heteroatom bonds using organo-alkali metal reagents, which are sustainable and practical protocols in synthetic chemistry.
Article
Chemistry, Organic
Yi-Bing Yin, Xiao-Shui Peng, Henry N. C. Wong
Summary: A one-pot iron-catalyzed cross-coupling protocol was developed for the synthesis of unsymmetrical biaryls using aryl chlorides, aryl bromides, and magnesium metal. The key step in this reaction is the in situ generation of Grignard reagents.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Hao-Ran Ma, Xiao-Shui Peng, Jian-Fang Cui, Henry Nai Ching Wong
Summary: Due to the configurational stabilities and unique properties of tetraphenylenes, extensive investigations have been conducted in their uses in various fields such as supramolecular chemistry, asymmetric catalysis, liquid crystalline materials, molecular devices, and organic light-emitting diodes. Recently, the emerging applications of chiral tetraphenylene-based ligands/catalysts in asymmetric catalysis and as chiral materials have renewed the interest of synthetic chemists. This perspective summarizes the synthetic advances and challenges of emerging optically active tetraphenylenes, and highlights their fascinating applications in asymmetric catalysis and chiral functional materials.
TETRAHEDRON LETTERS
(2023)
Review
Chemistry, Organic
Peng Chen, Hao-Nan Chen, Henry N. C. Wong, Xiao-Shui Peng
Summary: The development of transition-metal-catalyzed coupling reactions is an efficient strategy for the synthesis of carbon-carbon bonds in organic chemistry. Due to its cost-effectiveness and environmental sustainability, iron-catalyzed coupling reactions have gained increasing attention in recent years. This mini-review provides a systematic analysis of the formation of C(sp(2))-C(sp(2)) bonds through iron-catalyzed coupling reactions based on existing literature.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jia Guo, Hao-Ran Ma, Wen-Bin Xiong, Luoyi Fan, You-Yun Zhou, Henry N. C. Wong, Jian-Fang Cui
Summary: An efficient kinetic resolution of alkyl allylic alcohols has been achieved through an iridium-catalyzed enantioselective alkynylation reaction. The method allows for the synthesis of chiral 1,4-enynes with various functional groups and unreacted enantioenriched allylic alcohols. It is particularly effective for preparing optically pure alkyl allylic alcohols that are difficult to access via other asymmetric reactions.
Article
Chemistry, Organic
Peng Chen, Zhi-Yong Wang, Jia-Xin Wang, Xiao-Shui Peng, Henry N. C. Wong
Summary: Two efficient protocols for remote C(sp(3))-H activation involving palladium-catalyzed C(sp(3))-C(sp(2)) and C(sp(3))-C(sp) cross-coupling have been reported. The reactions utilize aryllithium reagents and terminal alkynes as key coupling partners and demonstrate high yields, good functional group tolerance, and high regioselectivities in more than 50 examples.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Jia Guo, Wen-Bin Xiong, Hao-Ran Ma, Luoyi Fan, You-Yun Zhou, Henry N. C. Wong, Jian-Fang Cui
Summary: A novel method involving chiral gold(III) complexation for optical resolution of (+/-)-1,16-dihydroxytetraphenylene (DHTP) is reported. This method offers several key advantages, including recyclability of chiral resolution reagents, scalability to gram quantities, and simplicity of operation. Using this method, optically pure DHTP was obtained, and a library of 2,15-diaryl (S)-DHTPs and several (S)-DHTP-derived phosphoramidite ligands were synthesized. Finally, the excellent performance of a (S)-DHTP phosphoramidite ligand in iridium-catalyzed asymmetric allylic alkynylation reactions was demonstrated.
