摘要:
<jats:p><jats:bold>Summary of main observation and conclusion</jats:bold></jats:p><jats:p>An enantioselective deoxygenative cyanation of benzyl alcohols was accomplished for the first time through the synergistic photoredox and copper catalysis. This reaction features the use of organic photosensitizer and low‐cost 3d metal catalyst, simple and safe operations, and extremely mild conditions. A variety of chiral benzyl nitriles were produced in generally good yields and high level of enantiocontrols from readily available feedstocks (22 examples, up to 93% yield and 92% ee).</jats:p>
通讯机构:
[Lu, LQ; Xiao, WJ] C;Cent China Normal Univ, Coll Chem, Minist Educ, Key Lab Pesticide & Chem Biol, 152 Luoyu Rd, Wuhan 430079, Hubei, Peoples R China.
摘要:
N-Heterocyclic carbenes (NHCs) are efficient Lewis basic catalysts for the umpolung of various polarized unsaturated compounds usually including aldehydes, imines, acyl chlorides and activated esters. NHC catalysis involving electron pair transfer steps has been extensively studied; however, NHC catalysis through single-electron transfer (SET) processes, despite having the potential to achieve chemical transformations of inert chemical bonds and using green reagents, has long been a challenging task in organic synthesis. In parallel, visible-light-induced photocatalysis and photoexcitation have been established as powerful tools to facilitate sustainable organic synthesis, as they enable the generation of various reactive radical intermediates under extremely mild conditions. Recently, a number of elegant visible-light-induced, NHC-catalyzed transformations were developed for accessing valuable organic compounds. As a result, this minireview will highlight the recent advances in this field.
摘要:
1,3,5-Trisubstituted 1,3,5-triazinanes (hexahydro-1,3,5-triazines), as stable and readily available surrogates for formaldimines, have found extensive applications for the construction of various nitrogen-containing compounds. The formaldimines, formed in situ from this reagent class, can participate in various aminomethylation and cycloaddition reactions. This short review presents recent advances in this field with emphasis on the conceptual ideas behind the developed methodologies and the reaction mechanisms.
1 Introduction
2 Aminomethylations with 1,3,5-Triazinanes
3 Cycloadditions with 1,3,5-Triazinanes
3.1 Use of 1,3,5-Triazinanes as Two-Atom Synthons
3.2 Use of 1,3,5-Triazinanes as Three-Atom Synthons
3.3 Use of 1,3,5-Triazinanes as Four-Atom Synthons
3.4 Use of 1,3,5-Triazinanes as Six-Atom Synthons
4 Conclusions
作者机构:
[Miao-Miao Li; Bao-Le Qu; Yu-Qing Xiao; Liang‐Qiu Lu; Wen‐Jing Xiao] CCNU-uOttawa Joint Research Centre Key Laboratory of Pesticide &Chemical Biology Ministry of Education College of Chemistry Central China Normal University 152 Luoyu Road Wuhan Hubei 430079 China;State Key Laboratory for Oxo Synthesis and Selective Oxidation Lanzhou Institute of Chemical Physics (LICP) Chinese Academy of Sciences Lanzhou 730000 P. R. China;[Qin Xiong] School of Chemistry and Chemical Engineering Chongqing University Chongqing 400030 China;College of Chemistry, and Institute of Green Catalysis Zhengzhou University Zhengzhou Henan 450001 China
通讯机构:
[Prof. Yu Lan] S;[Prof. Liang-Qiu Lu] C;CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China<&wdkj&>State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, 730000 P. R. China<&wdkj&>School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030 China<&wdkj&>College of Chemistry, and Institute of Green Catalysis, Zhengzhou University, Zhengzhou, Henan, 450001 China
摘要:
<jats:title>Abstract</jats:title><jats:p>Vinylcyclopropanes (VCPs) are commonly used in transition‐metal‐catalyzed cycloadditions, and the utilization of their recently realized reactivities to construct new cyclic architectures is of great significance in modern synthetic chemistry. Herein, a palladium‐catalyzed, visible‐light‐driven, asymmetric [5+2] cycloaddition of VCPs with α‐diazoketones is accomplished by switching the reactivity of the Pd‐containing dipolar intermediate from an all‐carbon 1,3‐dipole to an oxo‐1,5‐dipole. Enantioenriched seven‐membered lactones were produced with good reaction efficiencies and selectivities (23 examples, 52–92 % yields with up to 99:1 er and 12.5:1 dr). In addition, computational investigations were performed to rationalize the observed high chemo‐ and periselectivities.</jats:p>
摘要:
<jats:title>Abstract</jats:title><jats:p>A tandem phospha‐Michael addition/<jats:italic>N</jats:italic>‐acylation/intramolecular Wittig reaction of in situ formed aza‐<jats:italic>o</jats:italic>‐QMs is disclosed. This approach features high functional group tolerance and provides a convenient and practical access to biologically significant indole derivatives (37 examples, up to 91% yield) under mild reaction conditions.</jats:p><jats:p><jats:boxed-text content-type="graphic" position="anchor"><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/png" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/adsc202000343-toc-0001-m.png"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text>
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通讯作者:
Prof. Dr. Liang-Qiu Lu<&wdkj&>Prof. Dr. Wen-Jing Xiao<&wdkj&>Prof. Dr. Liang-Qiu Lu Prof. Dr. Liang-Qiu Lu Prof. Dr. Liang-Qiu Lu<&wdkj&>Prof. Dr. Wen-Jing Xiao Prof. Dr. Wen-Jing Xiao Prof. Dr. Wen-Jing Xiao
作者机构:
[Xuan Jiang; Mao-Mao Zhang; Wei Xiong; Prof. Dr. Liang-Qiu Lu; Xuan Jiang Xuan Jiang Xuan Jiang; Mao-Mao Zhang Mao-Mao Zhang Mao-Mao Zhang; Wei Xiong Wei Xiong Wei Xiong; Prof. Dr. Liang-Qiu Lu Prof. Dr. Liang-Qiu Lu Prof. Dr. Liang-Qiu Lu] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China;State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032 China;[Prof. Dr. Wen-Jing Xiao; Prof. Dr. Wen-Jing Xiao Prof. Dr. Wen-Jing Xiao Prof. Dr. Wen-Jing Xiao] Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China<&wdkj&>State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032 China
通讯机构:
[Prof. Dr. Liang-Qiu Lu; Prof. Dr. Wen-Jing Xiao; Prof. Dr. Liang-Qiu Lu Prof. Dr. Liang-Qiu Lu Prof. Dr. Liang-Qiu Lu; Prof. Dr. Wen-Jing Xiao Prof. Dr. Wen-Jing Xiao Prof. Dr. Wen-Jing Xiao] K;Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China<&wdkj&>Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079 China<&wdkj&>State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032 China
摘要:
<jats:title>Abstract</jats:title><jats:p>The palladium‐catalyzed Heck reaction is a well‐known, Nobel Prize winning transformation for producing alkenes. Unlike the alkenyl and aryl variants of the Heck reaction, the alkyl‐Heck reaction is still underdeveloped owing to the competitive side reactions of alkyl–palladium species. Herein, we describe the development of a deaminative alkyl‐Heck‐type reaction that proceeds through C−N bond activation by visible‐light photoredox catalysis. A variety of aliphatic primary amines were found to be efficient starting materials for this new process, affording the corresponding alkene products in good yields under mild reaction conditions. Moreover, this strategy was successfully applied to deaminative carbonylative alkyl‐Heck‐type reactions.</jats:p>
摘要:
The development of green and sustainable methods for “effective” synthesis of fine chemicals is an important goal for synthetic organic chemists. Oxidative reactions are an important process in Nature and constitute one of the most fundamental chemical transformations in organic synthesis. This chapter highlights the recent advances of visible-light-mediated aerobic oxidation and oxygenation reactions. The amine motif is a kind of good electron donor due to the nitrogen atom possessing lone pair electron, and they are the most common reductive quenchers for the photoredox catalysis, particularly tertiary amines. Visible-light-induced photocatalytic oxidation reactions of amines using oxygen as an oxidant have attracted significant interest from organic chemists. The photocatalytically generated imine intermediates have been applied into a series of nucleophilic addition and cycloaddition reactions. Transition metal-catalyzed C–H oxidative functionalization has proven to be a powerful tool for the construction of complex organic molecules.
作者机构:
黄冈师范学院催化材料制备及应用湖北省重点实验室化学化工学院黄冈438000;华中师范大学化学学院农药与化学生物学教育部重点实验室武汉430079;Department of Chemistry, Georgia State University, Atlanta, Georgia 30302-4098, United States