Article
Chemistry, Multidisciplinary
Chao Jiang, Pinhong Chen, Guosheng Liu
Summary: In this study, a novel reaction technique combining photocatalysis and copper catalysis was developed for the radical decarboxylative C(sp(3))-C(sp(3)) cross-coupling of NHPI esters and cyclopropanols, leading to the efficient synthesis of ss-benzyl ketones. The terpyridin-4'-one ligand played a vital role in the reaction by facilitating the capture of benzylic radicals by alkyl-copper species generated through the copper-catalyzed ring-opening of cyclopropanols. The reaction exhibited broad substrate scope and wide functional group compatibility, providing a new approach for C(sp3)-C(sp3) bond formation.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xinyan Zhou, Jin Hao, Yilin Kong, Runsheng Xu
Summary: An iron-catalyzed cascade reaction allows for the synthesis of various derivatives under mild conditions, providing an economical approach for C(sp(3))-Se bond formation starting from 1,2,3,4-tetrahydroisoquinolines and 2-hydroselenobenzoic acids.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Rhys A. Lippa, David J. Battersby, John A. Murphy, Tim N. Barrett
Summary: The synthesis of substituted arylethylamines via palladium-catalyzed coupling between (chloromethyl)aryls and N,N-dialkylaminomethyltrifluoroborate salts was reported in this study. Rapid hit identification was achieved using microscale high-throughput experimentation, followed by millimolar-scale reaction parameter optimization. A range of structurally and electronically varied arylethylamine products were obtained in moderate to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Paul J. Chirik
Summary: A cobalt-catalyzed method for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides was developed, with cobalt-ligand combinations being assessed through high-throughput experimentation. The use of cobalt(II) sources with trans-N,N'-dimethylcyclohexane-1,2-diamine (DMCyDA, L-1) resulted in optimal yield and selectivity. The transformation allowed for diverse steric and electronic properties on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile, with radical trap experiments supporting the formation of electrophile-derived radicals during catalysis.
Article
Chemistry, Organic
Xiaoqin Ning, Yongke Chen, Fangdong Hu, Ying Xia
Summary: This study presents the palladium-catalyzed cross-coupling reactions of cyclobutanone-derived N-sulfonylhydrazones with aryl or benzyl halides, demonstrating that the metal carbene process and beta-hydride elimination can occur smoothly in strained ring systems to yield structurally diverse products. The preliminary success in asymmetric carbene coupling reactions in strained ring systems offers a promising route for the synthesis of enantioenriched four-membered-ring molecules.
Article
Chemistry, Physical
Garrett P. R. Freure, Eric A. Skrotzki, Jean-Danick E. Lavertu, Stephen G. Newman
Summary: Various methods have been investigated recently for the arylation of weakly acidic C(sp(3))-H bonds, with this study focusing on a base-mediated approach using organometallic superbases. The study developed conditions for high selectivity metalation using either n-BuLi/diamine or n-BuLi/KOtBu superbases, allowing for direct use in cross-coupling or formation of organozincs for reactions with functional groupdense organohalides.
Article
Multidisciplinary Sciences
Wei Liu, Marissa N. Lavagnino, Colin A. Gould, Jesus Alcazar, David W. C. MacMillan
Summary: The S(H)2 mechanism has been utilized in the synthetic formation of organic molecules to create quaternary sp(3)-carbon centers. The mechanism involves distinguishing between primary and tertiary carbons to form S(H)2 bonds and generating radical classes simultaneously from abundant functional groups using photocatalysis.
Article
Chemistry, Organic
Yi-Fan Zhang, Han-Nan Chen, Yi Xiao, Zhencun Cui, Wei David Wang, Guo-Qiang Xu
Summary: Here, a novel protocol for synthesizing alpha-functionalized saturated aza-heterocycles is presented, allowing for the easy installation of various nucleophilic groups. Additionally, a range of biologically valuable 3,3'-diindolylmethane derivatives can be readily synthesized under mild photocatalytic conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ying Qin, Lianghui Li, Jin-Yuan Liang, Kailong Li, Dongbing Zhao
Summary: This method involves the first intermolecular silacyclization strategy with Pd-catalyzed silicon-based C(sp(2))-C(sp(3) cross-coupling, allowing the assembly of structurally novel and interesting sila-benzo[b]oxepines with good functional group tolerance. The key to success lies in the stronger affinity of silicon atoms for oxygen nucleophiles than carbon nucleophiles, as well as the inherent ring-strain-release Lewis acidity of silacyclobutanes (SCBs).
Article
Multidisciplinary Sciences
Haigen Fu, Jingzhe Cao, Tianzhang Qiao, Yuyin Qi, Simon J. Charnock, Samuel Garfinkle, Todd K. Hyster
Summary: This study reports a highly chemoselective and enantioselective Csp(3)-Csp(3) XEC reaction catalyzed by flavin-dependent 'ene'-reductases (EREDs). The photoexcitation of the enzyme-templated charge-transfer complex enables the chemoselective reduction of alkyl halides and high enantioselectivity.
Article
Chemistry, Multidisciplinary
Anirban Mondal, Paco Visser, Anna M. Doze, Jeffrey Buter, Ben L. Feringa
Summary: Organolithium-based cross-coupling reactions are essential for constructing C-C bonds, especially for coupling various organolithium reagents with aromatic (pseudo) halides. The reaction can be completed within 10 minutes at room temperature and is compatible with organolithium-sensitive functional groups, showing potential applications in the synthesis of key intermediates for pharmaceuticals, chemical biology, and natural products.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Tao Yang, Yi Wei, Ming Joo Koh
Summary: This new method allows for efficient synthesis of C-C bonds at ambient temperature, with site-selective cross-coupling capability and tolerance toward various functional groups sensitive to metal reductants.
Article
Chemistry, Organic
Ya-Ting Wen, Xiang-Tao Kong, Hong-Chao Liu, Cui-Tian Wang, Wan-Xu Wei, Bin Wang, Xue-Yuan Liu, Yong-Min Liang
Summary: An innovative 1,5-HAT cascade strategy has been proposed for nickel-catalyzed distal arylation via cross-electrophile coupling. It selectively activates the remote C(sp(3))-H bond through specific migration and uses Ar-I as the available electrophile for constructing the C(sp(3))-C(sp(2)) bond. The method shows broad applicability for benzylic and aliphatic N-fluorocarboxamides with yields up to 80%. Control experiments suggest that this reaction may be initiated by a radical process.
Article
Polymer Science
Xin Gao, Zeli Song, Jianfeng Hu, Hao Zhang
Summary: An efficient protocol for synthesizing sulfur-containing polymers without transition-metal catalyst has been developed. Various sulfur-containing polymers can be produced through cross coupling polymerization of Ntosylhydrazones and thiols in the presence of K2CO3. Additionally, a one-pot, two-step conversion from ketones to polymers offers an alternative and convenient route to form C-S linkages.
Article
Chemistry, Organic
Akash G. Tathe, Nitin T. Patil
Summary: This study reports C(sp(2))-S cross-coupling reactions of aryl iodides and arylsulfonyl hydrazides under ligand-enabled, Au(I)/Au(III) redox catalysis, highlighting the utility of this method for synthesizing various medicinally relevant biaryl sulfones without the need for prefunctionalized aryl coupling partners.
Article
Chemistry, Organic
Xiaoshen Ma, Seth B. Herzon
JOURNAL OF ORGANIC CHEMISTRY
(2016)
Article
Chemistry, Multidisciplinary
Xiaoshen Ma, Hester Dang, John A. Rose, Paul Rablen, Seth B. Herzon
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2017)
Article
Chemistry, Organic
Xiaoshen Ma, Roman Kucera, Olivia F. Goethe, Stephen K. Murphy, Seth B. Herzon
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Xiaoshen Ma, Seth B. Herzon
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Yiyi He, Chengsha Yuan, Zeqi Jiang, Li Shuai, Qing Xiao
Article
Chemistry, Organic
Sheng-Li Niu, Jiangtao Hu, Kuicheng He, Ying-Chun Chen, Qing Xiao
Article
Chemistry, Organic
Xiaoshen Ma, David L. Sloman, Yongxin Han, David J. Bennett
Review
Chemistry, Organic
Xiaoshen Ma, Luu Nhat Pham
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Xiaoshen Ma, Wilfredo Pinto, Luu N. Pham, David L. Sloman, Yongxin Han
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Zeqi Jiang, Sheng-Li Niu, Qiang Zeng, Qin Ouyang, Ying-Chun Chen, Qing Xiao
Summary: A novel Pd-catalyzed reaction has been developed for selective alkynylallylation of specific C-C sigma bonds in cyclopropenes, providing an efficient approach to highly functionalized dienynes. The reaction features fascinating atom and step economy and can produce gram-scale products using a simple, neutral, and low-cost catalytic system with high TONs. DFT calculations suggest that the success of the reaction relies on the selective insertion of cyclopropene double bonds into the C-Pd bond of ambidentate Pd complex and subsequent nonclassical beta-C elimination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xiaoshen Ma, Charles S. Yeung
Summary: Our study focused on achieving C(sp(2))-C(sp(3)) coupling reactions using 2,2-difluorobicyclo[1.1.1]pentane (BCP-F-2) building blocks. Through comparison of reactivities between BCP and BCP-F-2 analogues, we found that the Barluenga coupling reaction showed promising results, expanding the potential applications of BCP-F-2 in organic chemistry and medicinal chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xiaoshen Ma, Yuan Jiang
Summary: We have developed the first transition-metal-free synthesis of gem-diboromethyl-substituted bicyclo[1.1.1]pentane (BCP) and other related C(sp3)-rich carbocyclic benzene bioisosteres from their corresponding p-tosylhydrazones. These newly functionalized benzene bioisosteres show unique reactivities towards palladium-catalyzed C(sp2)-C(sp3) cross couplings, making them potentially useful in drug discovery for complex substrates.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Olivia L. Garry, Michael Heilmann, Jingjia Chen, Yufan Liang, Xiaheng Zhang, Xiaoshen Ma, Charles S. Yeung, David Jonathan Bennett, David W. C. MacMillan
Summary: Replacing aryl rings with saturated carbocyclic structures is of great interest in drug discovery for improved pharmacokinetic properties. However, the synthesis of 2-substituted BCPs remains challenging and nonmodular. This study presents a generalizable strategy for bridge functionalization and demonstrates a streamlined pathway to diverse 2-substituted BCPs through radical C-H abstraction and metallaphotoredox protocols.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xiaoshen Ma, Yuan Jiang
Summary: We describe a general transition-metal-free synthesis of gem-diboromethyl-substituted bicyclo[1.1.1]pentane (BCP) and other related C(sp(3))-rich carbocyclic benzene bioisosteres from their corresponding p-tosylhydrazones. These functionalized benzene bioisosteres exhibit unique reactivity towards palladium-catalyzed C(sp(2))-C(sp(3)) cross couplings. The overall transformation can be applied to complex substrates and has potential utility in drug discovery.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xiaoshen Ma, Yongxin Han, David J. Bennett
