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Recent Advances in the Addition of Amide/Sulfonamide Bonds to Alkynes

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Recent Advances in the Addition of Amide/Sulfonamide Bonds to Alkynes molecules Review Recent Advances in the Addition of Amide/Sulfonamide Bonds to Alkynes Fei Zhao 1 , Pinyi Li 1, Xiaoyan Liu 1, Xiuwen Jia 1, Jiang Wang 2,3 and Hong Liu 2,3,* 1 Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of Antibiotics, Chengdu University, 168 Hua Guan Road, Chengdu 610052, China; [email protected] (F.Z.); [email protected] (P.L.); [email protected] (X.L.); [email protected] (X.J.) 2 State Key Laboratory of Drug Research and CAS Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zuchongzhi Road, Shanghai 201203, China; [email protected] 3 University of Chinese Academy of Sciences, No.19A Yuquan Road, Beijing 100049, China * Correspondence: [email protected]; Tel.: +86-021-5080-7042 Academic Editor: Michal Szostak Received: 11 December 2018; Accepted: 27 December 2018; Published: 4 January 2019 Abstract: The addition of amide/sulfonamide bonds to alkynes is not only one of the most important strategies for the direct functionalization of carbon–carbon triple bonds, but also a powerful tool for the downstream transformations of amides/sulfonamides. The present review provides a comprehensive summary of amide/sulfonamide bond addition to alkynes, including direct and metal-free aminoacylation, based-promoted aminoacylation, transition-metal-catalyzed aminoacylation, organocatalytic aminoacylation and transition-metal-catalyzed aminosulfonylation of alkynes up to December 2018. The reaction conditions, regio- and stereoselectivities, and mechanisms are discussed and summarized in detail. Keywords: amide bond; sulfonamide bond; alkynes; addition reaction; aminoacylation; aminosulfonylation 1. Introduction The addition of atom–atom bonds to alkynes has become an important strategy for the functionalization of carbon–carbon triple bonds [1–16]. These intermolecular and intramolecular addition reactions provide a facile and efficient access to highly functionalized alkenes and cyclic compounds, respectively, in a high atom- and step-economic manner. Considering the large occurrence of amide/sulfonamide motifs in natural products and pharmaceutical agents, the addition of amide/sulfonamide bonds to alkynes, namely aminoacylation/aminosulfonylation of alkynes, is particularly important. Because they allow the direct downstream transformations of amides/sulfonamides by the insertion of carbon–carbon triple bonds into the amide/sulfonamide bonds, they thus produce more complex and skeletally different addition molecules (Scheme1). In addition, the aminoacylation/aminosulfonylation of alkynes also constitutes a tool for the structural modification of compounds carrying amide/sulfonamide bonds, especially for peptides, which are an important class of drugs used in the clinic [17–19]. Besides, amide/sulfonamide bond addition to alkynes, which constructs one C–C/S and one C–N bond in a single step featuring high atom- and step-economy, is in accordance with the concept of “green and sustainable chemistry”. It should be noted that the addition of amide/sulfonamide bonds to alkynes has not been reviewed before. Moreover, amide/sulfonamide bond addition to alkynes has achieved many important developments in recent decades, especially in transition-metal-catalyzed and organocatalytic processes. Therefore, a review focused on the aminoacylation/aminosulfonylation of alkynes Molecules 2019, 24, 164; doi:10.3390/molecules24010164 www.mdpi.com/journal/molecules Molecules 2019, 24, 164 2 of 22 Molecules 2018, 23, x FOR PEER REVIEW 2 of 22 Molecules 2018, 23, x FOR PEER REVIEW 2 of 22 alkynes would enrich the knowledge of synthetic chemists who are interested in amide/sulfonamide would enrich the knowledge of synthetic chemists who are interested in amide/sulfonamide bond activation. The aim of the present review is to provide a systematical and comprehensive alkynesbond activation. would enrich The the aim knowledge of the present of synthetic review chemists is to provide who are a systematical interested in and amide/sulfonamide comprehensive summary on the addition of amide/sulfonamide bonds to alkynes, including direct and catalyst‐free bondsummary activation. on the additionThe aim of of amide/sulfonamide the present review bonds is to provide to alkynes, a systematical including direct and and comprehensive catalyst-free aminoacylation, based‐promoted aminoacylation, transition‐metal‐catalyzed aminoacylation, summaryaminoacylation, on the addition based-promoted of amide/sulfonamide aminoacylation, bonds transition-metal-catalyzedto alkynes, including direct and aminoacylation, catalyst‐free organocatalytic aminoacylation, and transition‐metal‐catalyzed aminosulfonylation of alkynes up to aminoacylation,organocatalytic aminoacylation, based‐promoted and transition-metal-catalyzedaminoacylation, transition aminosulfonylation‐metal‐catalyzed aminoacylation, of alkynes up to December 2018. We hope this review will serve as a handy reference for chemists interested in the organocatalyticDecember 2018. aminoacylation, We hope this review and transition will serve‐metal as a‐ handycatalyzed reference aminosulfonylation for chemists interestedof alkynes inup the to addition of amide/sulfonamide bonds to alkynes, and will encourage further developments in this Decemberaddition of 2018. amide/sulfonamide We hope this review bonds will to alkynes, serve as anda handy will encouragereference for further chemists developments interested inin thisthe field in overcoming the remaining challenges. additionfield in overcoming of amide/sulfonamide the remaining bonds challenges. to alkynes, and will encourage further developments in this field in overcoming the remaining challenges. Scheme 1. The addition of amide/sulfonamide bonds to alkynes. Scheme 1.1. The addition of amide/sulfonamide bonds bonds to to alkynes. alkynes. 2. Addition of Amide Bonds to Alkynes 2. Addition of Amide Bonds to Alkynes 2. Addition of Amide Bonds to Alkynes 2.1. Direct Addition of Amide Bonds to Alkynes without Catalysts and Additives 2.1. Direct Addition of Amide Bonds to Alkynes without Catalysts and Additives 2.1. DirectThe first Addition example of Amide of amide Bonds bond to Alkynes addition without to alkynes Catalysts was and a catalyst Additives‐ and additive‐free process as The first example of amide bond addition to alkynes was a catalyst- and additive-free process as reportedThe firstby E exampleğe’s group of inamide 1976 bond [20]. Theyaddition found to alkynes the treatment was a catalystof active‐ and2‐phenylpyrazolidin additive‐free process‐3‐ones as reported by E˘ge’sgroup in 1976 [20]. They found the treatment of active 2-phenylpyrazolidin-3-ones 4 reported4 with dimethyl by Eğe’s groupacetylenedicarboxylate in 1976 [20]. They 5found in CH the3CN treatment under ofreflux active led 2‐phenylpyrazolidin to the formation‐ 3of‐ones the with dimethyl acetylenedicarboxylate 5 in CH3CN under reflux led to the formation of the interesting 4interesting with dimethyl ring expansion acetylenedicarboxylate products 1,2‐diazepin 5 in CH‐5‐3onesCN 6under, albeit reflux with unsatisfactoryled to the formation selectivities of andthe ring expansion products 1,2-diazepin-5-ones 6, albeit with unsatisfactory selectivities and yields interestingyields (Scheme ring 2).expansion The main products byproducts 1,2‐diazepin of this reaction‐5‐ones were 6, albeit the ciswith‐ and unsatisfactory trans‐ Michael selectivities‐type addition and (Scheme2). The main byproducts of this reaction were the cis- and trans- Michael-type addition yieldsproducts. (Scheme Besides, 2). The this main transformation byproducts of was this stronglyreaction wereinfluenced the cis‐ andby the trans solvent‐ Michael used.‐type Polar addition but products. Besides, this transformation was strongly influenced by the solvent used. Polar but nonprotic products.nonprotic Besides,solvents suchthis transformationas acetone and wasacetonitrile strongly gave influenced the best byresults the whilesolvent few used. products Polar were but solvents such as acetone and acetonitrile gave the best results while few products were obtained nonproticobtained insolvents protic suchsolvents as acetone such asand ethanol. acetonitrile Similar gave results the best were results also while observed few products in Svete were and in protic solvents such as ethanol. Similar results were also observed in Svete and Stanovnik’s obtainedStanovnik in′s proticresearch solvents on thesuch additionas ethanol. reactions Similar resultsbetween were 5,5 ‐alsodimethyl observed‐2‐(1H in‐indenyl Svete ‐2)and‐3‐ research on the addition reactions between 5,5-dimethyl-2-(1H-indenyl-2)-3-pyrazolidinones 7 and Stanovnikpyrazolidinones′s research 7 and acetylenedicarboxylateson the addition reactions 8 (Scheme between 3) [21]. 5,5A plausible‐dimethyl ‐reaction2‐(1H‐indenyl mechanism‐2)‐3‐ acetylenedicarboxylates 8 (Scheme3)[ 21]. A plausible reaction mechanism was outlined in Scheme4. pyrazolidinoneswas outlined in7 andScheme acetylenedicarboxylates 4. The Michael 8 (Schemeaddition 3) of[21]. N1 A plausibleof the reactionpyrazolidinones mechanism to The Michael addition of N1 of the pyrazolidinones to acetylenedicarboxylate generates the carbanionic wasacetylenedicarboxylate outlined in Scheme generates 4. theThe carbanionic Michael intermediateaddition of 11N1, which of attacksthe pyrazolidinones the carbonyl group to intermediate 11, which attacks the carbonyl group across the ring to give the bicyclic amino-acetal
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