Article
Chemistry, Physical
Netgie Laguerre, Paul S. Riehl, Daniel G. Oblinsky, Megan A. Emmanuel, Michael J. Black, Gregory D. Scholes, Todd K. Hyster
Summary: This study presents a novel photoenzymatic allylation method for the synthesis of cyclic lactams with high enantioselectivity. The termination of the reaction via the cleavage of the silyl group to generate a silyl radical represents a distinct mechanism compared to traditional radical allylations, demonstrating the potential of EREDs.
Article
Chemistry, Physical
Kai Sun, Masato Ueno, Keisuke Imaeda, Kosei Ueno, Masaya Sawamura, Yohei Shimizu
Summary: A boron-catalyzed alpha-allylation of carboxylic acids with allylsulfones under blue LED irradiation conditions has been developed. The photoexcitation of catalytically generated boron enediolates induces single-electron transfer to the allylsulfones, leading to subsequent C-C bond formation and the construction of sterically demanding quaternary carbon centers at the position a to the carboxy group. The p-extended ligand on the boron atom is likely crucial for the efficient photoexcitation of the boron enediolates.
Article
Chemistry, Physical
Sharad Kumbhar, Chinpiao Chen
Summary: Asymmetric allylation and vinylation of aldehydes using chromium(II)-oxazoline catalyst have been achieved, leading to high yields and enantioselectivity of homoallylic alcohols and allylic alcohols. The developed protocol offers a reliable and milder method for preparing chiral homoallylic and allylic alcohols.
CATALYSIS COMMUNICATIONS
(2021)
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
Chemistry, Organic
Zhu Cao, Huihui Zhang, Xinxin Wu, Yahong Li, Chen Zhu
Summary: The research achieved the heteroarylation of unactivated aliphatic C-H bonds through radical-mediated heteroaryl migration, leading to a variety of heteroaryl-substituted aliphatic ketones. The method is applicable to O-/S-/N-containing heteroaryls and features mild C-C bond cleavage and good selectivity for tertiary C-H bonds.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Physical
Netgie Laguerre, Paul S. Riehl, Daniel G. Oblinsky, Megan A. Emmanuel, Michael J. Black, Gregory D. Scholes, Todd K. Hyster
Summary: This study presents a photoenzymatic allylation method for the synthesis of alpha-chloroamides using allyl silanes, resulting in high enantioselectivity in the formation of lactams. The mechanism involves radical termination via beta-scission of a silyl group, which differs from traditional radical allylations. This alternative strategy utilizing flavin-dependent ene-reductases shows the potential for catalyzing radical termination reactions beyond hydrogen atom transfer.
Article
Multidisciplinary Sciences
Guogang Deng, Shengzu Duan, Jing Wang, Zhuo Chen, Tongqi Liu, Wen Chen, Hongbin Zhang, Xiaodong Yang, Patrick J. Walsh
Summary: In this study, a transition-metal-free allylation strategy with allyl ether electrophiles is demonstrated to form homoallylic amine derivatives in up to 92% yield, providing valuable insights into C(sp(3))-C(sp(3)) bond-forming reactions.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Zhen Wu, Yaohui Xu, Huihui Zhang, Xinxin Wu, Chen Zhu
Summary: This study reveals an efficient and practical method for synthesizing sulfonyl alkynyl/allyl/cyano-substituted BCP derivatives through a novel radical-mediated difunctionalization of propellane, with broad functional group tolerance, high product diversity, gram-scale preparation, and excellent atom-economy.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Organic
Beatrice Quiclet-Sire, Samir Z. Zard
Summary: This article summarizes the routes to tetralones, tetralines, and naphthalenes based on the xanthate chemistry developed in the authors' laboratory. The reversible transfer of xanthates allows radical additions to unactivated alkenes and tolerates a wide range of functional groups, including common polar groups. Xanthates also enable radical ring closures onto aromatic rings, offering a convergent approach to building blocks relevant to pharmaceutical, agrochemical, and material sciences.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Xingxuan Xia, Xi Chen, Binlin Zhao, Yu Yuan
Summary: An iron-catalyzed radical-mediated ring opening of cycloketoxime promoted by diboron compound is described, which offers alternative catalytic routes for selective C-C bond vinylation, enabling the preparation of diverse distal-cyanoalkyl alkenes. Experimental investigations demonstrate the crucial role of the diboron reagent during the catalytic cycle, and a reasonable mechanism is proposed.
Article
Chemistry, Organic
Xiaoping Chen, Xiaosheng Luo, Ping Wang
Summary: The direct activation of 4-alkyl DHPs via single electron transfer at the anode has been reported, leading to the synthesis of radical allylation products with different alkyl substituents.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Xue-Hua Deng, Jia-Xi Jiang, Qin Jiang, Ting Yang, Bo Chen, Long He, Wen-Dao Chu, Cheng-Yu He, Quan-Zhong Liu
Summary: In this study, the asymmetric cross reductive coupling reaction of conjugated dienes and ketoimines using copper hydride as a catalyst was achieved for the first time. The reaction, catalyzed by chiral Ph-BPE ligand, provides a rapid and efficient access to homoallylic amines with two vicinal stereogenic centers.
Article
Polymer Science
Quan-Xi Shi, Qian Li, Hang Xiao, Xiao-Li Sun, Hongli Bao, Wen-Ming Wan
Summary: This study demonstrates a versatile approach, called Barbier single-atom polymerization, for the utilization of monofunctional carboxylic acid resources to prepare polymers with specific luminescent properties. The synthesized polymers have potential applications in material science, artificial light-harvesting systems, and explosive detection.
Article
Chemistry, Multidisciplinary
Veerasikku Gopal Deepagan, Meike N. Leiske, Nicholas L. Fletcher, David Rudd, Terence Tieu, Nicholas Kirkwood, Kristofer J. Thurecht, Kristian Kempe, Nicolas H. Voelcker, Anna Cifuentes-Rius
Summary: Introduction of xanthate-functionalized poly(cyclic imino ethers)s (PCIEs) provides a new method for synthesizing highly monodisperse and fluorescent gold nanoclusters (AuNCs). These PCIE-AuNCs exhibit good colloidal stability, biocompatibility, and antifouling properties, showing potential for various theranostic applications.
Article
Chemistry, Organic
Fusheng Li, Shuangjie Lin, Xiyu Li, Lei Shi
Summary: This study introduces a novel radical strategy for the photocatalytic generation of pi-allyltitanium complexes from butadiene, enabling the direct three-component allylation of carbonyls. This environmentally benign approach provides rapid access to valuable homoallylic alcohols with exceptional regio- and diastereoselectivity control.
SYNTHESIS-STUTTGART
(2021)
