State Key Laboratory of Organometallic Chemistry

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSome Typical Advances in the Synthetic Applications of AllenesShengming MaView Author Information Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, People's Republic of China, and State Key Laboratory of Organometallic Chemistry, Chinese Academy of Scienceds, 354 Fenglin Lu, Shanghai 200032, People's Republic of China Cite this: Chem. Rev. 2005, 105, 7, 2829–2872Publication Date (Web):June 9, 2005Publication History Received14 January 2005Published online9 June 2005Published inissue 1 July 2005https://pubs.acs.org/doi/10.1021/cr020024jhttps://doi.org/10.1021/cr020024jresearch-articleACS PublicationsCopyright © 2005 American Chemical SocietyRequest reuse permissionsArticle Views12337Altmetric-Citations1269LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Allenes,Chemical reactions,Cyclization,Hydrocarbons,Selectivity Get e-Alerts

Developing recyclable polymers provides a solution to materials' end-of-life issues and also an approach to establish a circular materials economy.

Phenols are widely used as starting materials in both industrial and academic society. Dearomatization reactions of phenols provide an efficient way to construct highly functionalized cyclohexadienones. The main challenge to make them asymmetric by catalytic methods is to control the selectivity while overcoming the loss of aromaticity. In this tutorial review, an up to date summary of recent progress in CADA reactions of phenol and aniline derivatives is presented.

Transition metal-catalyzed substitution of alcohols by N-nucleophiles (or N-alkylation of amines and related compounds with alcohols) avoids the use of alkylating agents by means of borrowing hydrogen (BH) activation of the alcohol substrates. Water is produced as the only by-product, which makes the "BH" processes atom-economic and environmentally benign. Diverse types of homogeneous organometallic and heterogeneous transition metal catalysts, and substrates such as N-nucleophiles including amines, amides, sulfonamides and ammonia, and various alcohols, can be used for this purpose, demonstrating the promising potential of "BH" processes to replace the procedures using traditional alkylating agents in pharmaceutical and chemical industries. Borrowing hydrogen activation of alcohols for C-N bond formation has recently been paid more and more attention, and a lot of new and novel procedures and examples have been documented. This critical review summarizes the recent advances in "BH" substitution of alcohols by N-nucleophiles since 2009. "Semi-BH" N-alkylation processes with or without an external hydrogen acceptor are also briefly presented. Suitable discussion of the "BH" strategy provides new principles for establishing green processes to replace the relevant traditional synthetic methods for C-N bond formation.

Although the chemistry of Pd(0), Pd(I) and Pd(II) is well established, high oxidation state Pd(IV) complexes are less well-known. This situation has highly changed in recent years. Many well-defined Pd(IV) complexes has been isolated and characterized, providing evidence for a series of proposed Pd(II)/Pd(IV) catalytic reactions. A deep understanding of the behavior of Pd(IV) complexes could lead to the design and development of novel reactions that could not be accessed by traditional Pd(0)/Pd(II) chemistry. This critical review describes the stoichiometric reactions of Pd(IV) complexes and discusses their potential mechanism in catalytic reactions (137 references).

Allenes have proven themselves to be valuable building blocks toward complex molecular targets, revealing novel applications in natural product synthesis, pharmaceutical chemistry and materials science. The ongoing interest in allene chemistry results in a variety of new methodologies and pathways for the synthesis of allenes. This feature article highlights some of the recent important developments on the synthesis of allenes and the applications on the synthesis of allenic natural products and allenic-based optoelectronic materials.

A novel Cu-catalyzed oxidative amidation-diketonization reaction of terminal alkynes leading to alpha-ketoamides has been developed. This chemistry offers a valuable mechanistic insight into this novel Cu catalysis via a radical process. O(2) not only participates as the ideal oxidant but also undergoes dioxygen activation under ambient conditions in this transformation.

Highly regioselective C-H functionalization/halogenation of acetanilides to produce ortho-haloacetanilides was catalyzed by Pd(OAc)2 and Cu(OAc) 2 with CuX2 as the halogen source.

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTOrtho Arylation of Acetanilides via Pd(II)-Catalyzed C−H FunctionalizationShangdong Yang, Bijie Li, Xiaobing Wan, and Zhangjie ShiView Author Information Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Green Chemistry Center, Peking University, Beijing 100871, and State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China Cite this: J. Am. Chem. Soc. 2007, 129, 19, 6066–6067Publication Date (Web):April 25, 2007Publication History Received2 February 2007Published online25 April 2007Published inissue 1 May 2007https://pubs.acs.org/doi/10.1021/ja070767shttps://doi.org/10.1021/ja070767srapid-communicationACS PublicationsCopyright © 2007 American Chemical SocietyRequest reuse permissionsArticle Views8790Altmetric-Citations359LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information SUBJECTS:Anions,Arylation,Functionalization,Phenyls,Reagents Get e-Alerts

Covering: 2000 up to 2019. Catalytic asymmetric dearomatization (CADA) reactions have witnessed considerable development in recent years. As the most extensively studied sub-branch, asymmetric dearomatization reactions of indole derivatives have attracted particular interest from the synthetic organic community since the molecular complexity can be rapidly enhanced with this method and the asymmetric total synthesis of a series of alkaloid natural products may be achieved with this strategy. In this review, we present the recent contributions in this dynamic area. The synthetic details are documented according to their different dearomative cyclization strategies.

We summarize in this review the recent development of chiral phosphoric acid (CPA)-catalyzed asymmetric dearomatization reactions. A wide array of electron-rich arenes (indoles, phenols, naphthols, benzothiophenes, benzofurans, etc.) and electron-poor arenes (pyridines, quinolines, isoquinolines, etc.) has been proved reactive towards various reaction partners in the presence of a CPA catalyst, enabling asymmetric dearomatization reactions that lead to structurally-diverse polycyclic molecules. The reactions are grouped according to the roles of the arenes in the reactions (as nucleophiles or electrophiles) and the types of reaction partners. This review closes with a personal perspective on the dynamic research area of asymmetric dearomatization reactions by CPAs.

Carbon-sulfur bond cross-coupling has become more and more attractive as an alternative protocol to establish carbon-carbon and carbon-heteroatom bonds. Diverse transformations through transition-metal-catalyzed C-S bond activation and cleavage have recently been developed. This review summarizes the advances in transition-metal-catalyzed cross-coupling via carbon-sulfur bond activation and cleavage since late 2012 as an update of the critical review on the same topic published in early 2013 (Chem. Soc. Rev., 2013, 42, 599-621), which is presented by the categories of organosulfur compounds, that is, thioesters, thioethers including heteroaryl, aryl, vinyl, alkyl, and alkynyl sulfides, ketene dithioacetals, sulfoxides including DMSO, sulfones, sulfonyl chlorides, sulfinates, thiocyanates, sulfonium salts, sulfonyl hydrazides, sulfonates, thiophene-based compounds, and C[double bond, length as m-dash]S functionality-bearing compounds such as thioureas, thioamides, and carbon disulfide, as well as the mechanistic insights. An overview of C-S bond cleavage reactions with stoichiometric transition-metal reagents is briefly given. Theoretical studies on the reactivity of carbon-sulfur bonds by DFT calculations are also discussed.

Compared with the traditional Grignard reaction, direct insertion of polar double bonds to C–H bonds<italic>via</italic>transition-metal catalysis is ideal from the viewpoint of atom-, step- and cost-economy and the avoidance of the waste emission, as well as of the complex manipulation of sensitive reagents.

Ruthenium-catalyzed oxidative C-H bond olefination of N-methoxybenzamides using an oxidizing directing group with a broad substrate scope is reported. The reactions of N-methoxybenzamides with acrylates in MeOH and styrene (or norbornadiene) in CF(3)CH(2)OH afforded two types of products.

Sulfonyl-derived functional groups can be found in a broad range of natural products, pharmaceuticals, and materials. Among the methods for the introduction of the sulfonyl group into small molecules, the approach using sulfur dioxide is the most promising and attractive one. In the past several years, the insertion of sulfur dioxide into small molecules under transition metal catalysis or metal-free conditions via a radical process has been developed. In this review, recent advances in the insertion of sulfur dioxide are presented.

Recent advances in photoinduced trifluoromethylation and difluoroalkylation under photocatalysis are summarized. Most of the photoredox reactions proceed efficiently under mild conditions with simple operation. Various fluorinated reagents are developed and applied in different transformations.

C-H bonds are ubiquitous in organic molecules. Homogenous gold-catalyzed direct functionalization of unsaturated C-H bonds has emerged as a powerful method in our synthetic toolbox. However, Csp(3)-H bonds have larger dissociation energy and lower proton acidity, and thus the efficient and exquisitely selective cleavage of this kind of chemical bonds for the formation of new carbon-carbon and carbon-heteroatom bonds is still a great challenge. In this tutorial review, we will highlight the recent achievements of gold-catalyzed oxidative and redox-neutral Csp(3)-H bond functionalization, which opens new avenues for economical and sustainable construction of fine chemicals.

A visible-light initiated oxidative cyclization of phenyl propiolates with sulfinic acids has been developed. The arylsulfonylation of alkynes was performed at room temperature under metal-free conditions to generate coumarin derivatives with wide functional group tolerance, good yields and high regioselectivity.

Iron-catalyzed cross-coupling of alkenyl/aryl carboxylates with primary alkyl Grignard reagent was described. This reaction brought a new family of electrophiles to iron catalysis. The combination of an inexpensive carboxylate electrophile and an iron catalyst would generate ample advantages.

A novel, efficient oxidation of α-aryl halogen derivatives to the corresponding α-aryl carbonyl compounds at room temperature has been disclosed. Natural sunlight and air are successfully utilized in this approach through the combination of photocatalysis and organocatalysis. A plausible mechanism was proposed on the basis of the mechanistic studies.