Co-reporter:Xing-Wang Lan;Yalan Xing
European Journal of Organic Chemistry 2017 Volume 2017(Issue 39) pp:5821-5851
Publication Date(Web):2017/10/25
DOI:10.1002/ejoc.201700678
Direct difunctionalization of simple alkenes, the incorporation of two functional groups onto a carbon–carbon double bond, is of particular interest to the chemical community owing to its important applications in organic synthesis. Mechanistically, two types of reactions – metal-catalyzed nucleophilic difunctionalization and radical difunctionalization – dominate this research field. Radical difunctionalization is more appealing from a synthetic perspective than metal-catalyzed nucleophilic difunctionalization because it allows the conversion of simple alkenes into complex molecules in a rapid and convenient manner. Furthermore, radical difunctionalization allows addition to simple alkenes by various carbon-centered radicals and even heteroatom-centered radicals. This review gives an overview of intermolecular and intramolecular radical difunctionalization of simple alkenes, with an emphasis on the reaction patterns and mechanisms, as well as potential applications in synthetic chemistry.
Co-reporter:Xing-Wang Lan, Nai-Xing Wang, Cui-Bing Bai, Cui-Lan Lan, Tong Zhang, Shi-Lu Chen, and Yalan Xing
Organic Letters 2016 Volume 18(Issue 23) pp:5986-5989
Publication Date(Web):November 11, 2016
DOI:10.1021/acs.orglett.6b02692
The first example of a metal-free unactivated C(sp3)–H bond functionalization of alkyl nitriles with terminal vinylarenes to provide γ-ketonitrile derivatives is described. This protocol features simple operations, a broad substrate scope, and atom and step economy. In addition, Cu-catalyzed C(sp3)–H bond functionalization of azodiisobutyronitrile (AIBN) and analogues with terminal vinylarenes to generate γ-ketonitriles was also studied. A preliminary free-radical pathway was confirmed by capturing an alkyl radical, and a conjugate system was found that can stabilize radical intermediates and be in favor of this transformation. Density functional theory (DFT) calculations also provide important evidence of the free-radical pathway.
Co-reporter:Xing-Wang Lan, Nai-Xing Wang, Wei Zhang, Jia-Long Wen, Cui-Bing Bai, Yalan Xing, and Yi-He Li
Organic Letters 2015 Volume 17(Issue 18) pp:4460-4463
Publication Date(Web):September 8, 2015
DOI:10.1021/acs.orglett.5b02116
A novel copper/manganese cocatalyzed direct oxidative coupling of terminal vinylarenes with ketones via C(sp3)–H bond functionalization following C–C bond formation has been developed using tert-butyl hydroperoxide as the radical initiator. Various ketones underwent a free-radical addition of terminal vinylarenes to give the corresponding 1,4-dicarbonyl products with excellent regioselectivity and efficiency through one step. A possible reaction mechanism has been proposed.
Co-reporter:Wei Zhang;Yanjing Wang;Cuibing Bai;Jialong Wen;Naixing Wang
Chinese Journal of Chemistry 2015 Volume 33( Issue 4) pp:401-404
Publication Date(Web):
DOI:10.1002/cjoc.201400836
Abstract
A novel and concise method for the construction of γ-nitro ketones and 1,3-dinitro compounds with chemoselective acyl transfer has been presented under basic conditions via one-pot reactions. These reactions feature high atom- and step-economic possess, mild condition and simple operation for one-pot synthesis of aliphatic nitro compounds. This protocol provides the products in good yields. The possible reaction mechanism has also been proposed.
Co-reporter:Yalan Xing, Nai-Xing Wang
Coordination Chemistry Reviews 2012 Volume 256(11–12) pp:938-952
Publication Date(Web):June 2012
DOI:10.1016/j.ccr.2012.01.002
This review focuses on recent progress in organocatalytic and metal-mediated asymmetric [3 + 2] cycloadditions, including ‘click’ chemistry, asymmetric 1,3-dipolar and asymmetric non-1,3-dipolar [3 + 2] cycloadditions. The theoretical aspects and synthetic applications of these organocatalytic and metal-mediated asymmetric [3 + 2] cycloadditions are summarized. In addition, an understanding of the mechanistic details which lead to efficient stereoselectivity in organocatalytic and metal-mediated asymmetric [3 + 2] cycloadditions is provided. Most of the references reviewed in this paper are from 2007 upto now.Highlights► 1,3-Dipolar reactions subject to both concerted reaction mechanism and the stepwise mechanism. ► Click chemistry is not a concerted 1,3-dipolar cycloaddition but a stepwise copper(I)-catalyzed process. ► Theoretical aspects and synthetic applications of these organocatalytic and metal-mediated asymmetric [3 + 2] cycloadditions are summarized. ► FMO theory to the reactivity of concerted 1,3-dipolar cycloadditions is reviewed.
Co-reporter:Zhong Huang;Jingchang Zhang;Yuqiang Zhou
European Journal of Organic Chemistry 2011 Volume 2011( Issue 5) pp:843-847
Publication Date(Web):
DOI:10.1002/ejoc.201001455
Abstract
Friedel–Crafts alkylation reactions of ethyl glyoxylate with various thiophenes to give the corresponding chiral secondary alcohols were demonstrated. The majority of these reactions proceeded with good enantioselectivities (up to 91 %) and satisfactory isolated yields. Notably, we found that 2-substituted thiophenes underwent the reaction more smoothly than unsubstituted and 3-substituted thiophenes.
Co-reporter:Nai-Xing Wang;Jia Zhao
Advanced Synthesis & Catalysis 2009 Volume 351( Issue 18) pp:3045-3050
Publication Date(Web):
DOI:10.1002/adsc.200900610
Abstract
A novel chiral nicotinamide adenine dinucleotide hydrogen (NADH) model with C3 symmetry was designed and synthesized. Hydrogens at the C-4 position of all dihydropyridine rings in the inner part of the bowl could transfer to the substrate with powerful enantioselectivity. This novel C3 symmetrical NADH model is capable of fluorescence emission at 455 nm when excited at 390 nm.