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Difunctionalization of Alkenes and Alkynes Via Intermolecular Radical and Nucleophilic Additions

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Difunctionalization of Alkenes and Alkynes Via Intermolecular Radical and Nucleophilic Additions molecules Review Difunctionalization of Alkenes and Alkynes via Intermolecular Radical and Nucleophilic Additions Hongjun Yao 1,†, Wenfei Hu 2,† and Wei Zhang 2,* 1 College of Biological Science and Technology, Beijing Forestry University, 35 Qinghua East Road, Beijing 100083, China; [email protected] 2 Department of Chemistry, University of Massachusetts Boston, 100 Morrissey Boulevard, Boston, MA 02125, USA; [email protected] * Correspondence: [email protected]; Tel.: +1-617-287-6147 † These authors contributed equally to this work. Abstract: Popular and readily available alkenes and alkynes are good substrates for the preparation of functionalized molecules through radical and/or ionic addition reactions. Difunctionalization is a topic of current interest due to its high efficiency, substrate versatility, and operational simplicity. Presented in this article are radical addition followed by oxidation and nucleophilic addition reactions for difunctionalization of alkenes or alkynes. The difunctionalization could be accomplished through 1,2-addition (vicinal) and 1,n-addition (distal or remote) if H-atom or group-transfer is involved in the reaction process. A wide range of moieties, such as alkyl (R), perfluoroalkyl (Rf), aryl (Ar), hydroxy (OH), alkoxy (OR), acetatic (O2CR), halogenic (X), amino (NR2), azido (N3), cyano (CN), as well as sulfur- and phosphorous-containing groups can be incorporated through the difunctional- ization reactions. Radicals generated from peroxides or single electron transfer (SET) agents, under photoredox or electrochemical reactions are employed for the reactions. Keywords: difunctionalization; radical; nucleophilic; alkene; alkyne; photoredox; single electron transfer; vicinal-difunctionalization; distal-difunctionalization; photoredox; electrochemical reaction Citation: Yao, H.; Hu, W.; Zhang, W. Difunctionalization of Alkenes and Alkynes via Intermolecular Radical and Nucleophilic Additions. 1. Introduction Molecules 2021, 26, 105. https:// Radical-based reactions such as homolytic bond cleavage, single electron transfer, doi.org/10.3390/molecules26010105 atom or group transfer, radical addition, and radical coupling processes are important Academic Editor: Derek J. McPhee organic transformations. In addition to the success of radical polymerization for making Received: 7 December 2020 synthetic polymers, organic radical reactions have also become an increasing important Accepted: 24 December 2020 tools for preparation of small molecules through radical addition, cyclization, cascade bond Published: 28 December 2020 formation, H-atom and group-transfer, and radical-radical coupling reactions [1,2]. Active researches on direct C-H bond functionalization [3], remote (distal) functionalization [4], Publisher’s Note: MDPI stays neu- Smile-type ipso-group rearrangement [5], cascade reaction [6], photoredox catalysis [7], and tral with regard to jurisdictional clai- electrochemical reaction [8] have significantly fueled the chemistry of synthetic radicals. ms in published maps and institutio- Radical difunctionalization of unsaturated carbon-carbon bonds is a topic of cur- nal affiliations. rent interest due to its high synthetic efficiency, substrate versatility, and operational simplicity [9–17]. Presented in this article are one-pot radical addition, oxidation and nucleophilic addition reactions to incorporate two functional groups to alkenes or alkynes. The difunctionalization could be accomplished through direct 1,2-addition (Scheme1I-A), Copyright: © 2020 by the authors. Li- 1,2-functionalization involving Smiles-type ispo aryl group migration (Scheme1I-B) [ 4,5], or censee MDPI, Basel, Switzerland. 1,n-functionalization involving H-atom transfer (Scheme1I-C) [ 4–6]. The majority examples This article is an open access article distributed under the terms and con- in this paper are direct 1,2-additions. Only a few cases are related to 1,2-functionalization ditions of the Creative Commons At- through Smiles-type rearrangement and distal difunctionalizations through 1,5-H-atom tribution (CC BY) license (https:// transfer. A wide range of moieties, such as alkyl (R), perfluoroalkyl (Rf), aryl (Ar), hydroxy 2 creativecommons.org/licenses/by/ (OH), alkoxy (OR), acetatic (O2CRRCO2), halogenic (X), amino (NR ), azido (N3), cyano 4.0/). (CN), as well as sulfur- and phosphorous-containing groups can be incorporated through Molecules 2021, 26, 105. https://doi.org/10.3390/molecules26010105 https://www.mdpi.com/journal/molecules Molecules 2021, 26, 105 2 of 31 transfer. A wide range of moieties, such as alkyl (R), perfluoroalkyl (Rf), aryl (Ar), hydroxy (OH), alkoxy (OR), acetatic (O2CRRCO2), halogenic (X), amino (NR2), azido (N3), cyano Molecules 2021, 26, 105 2 of 31 (CN), as well as sulfur- and phosphorous-containing groups can be incorporated through difunctionalization reactions. Radical reactions initiated with peroxides (such as dicumyl peroxide (DCP), di-t-butyl peroxide (DTBP), and t-butyl hydroperoxide (TBHP)) [18], pro- difunctionalization reactions. Radical reactions initiated with peroxides (such as dicumyl moted by single electron transfer agents (such as hypervalent iodine reagents (HIRs), ceric peroxide (DCP), di-t-butyl peroxide (DTBP), and t-butyl hydroperoxide (TBHP)) [18], promotedammoniumby singlenitrate electron (CAN), transfer Mn(OAc) agents2, and (such Na as2S hypervalent2O5), under iodinephotoredox reagents catalysis (HIRs), (such as Ru(bpy)3Cl2 and Ir(ppy)3) [7], and by electrochemical reactions [8] are included. In the rad- ceric ammonium nitrate (CAN), Mn(OAc)2, and Na2S2O5), under photoredox catalysis (suchical-initiated as Ru(bpy) difunctionalization3Cl2 and Ir(ppy)3)[ 7reactions,], and by electrochemical the catalysts reactionsare critical [8] for are included.oxidative SET to Inconvert the radical-initiated the intermediate difunctionalization radicals to carbocatio reactions,ns thefor catalyststhe sequential are critical reaction for oxida- with nucleo- tivephiles. SET to convert the intermediate radicals to carbocations for the sequential reaction with nucleophiles.This paper covers difunctionalization reactions which are initiated with a radical ad- ditionThis and paper ended covers with difunctionalization a nucleophilic addition. reactions whichIt is organized are initiated based with on a radical the nature addi- of initial tion and ended with a nucleophilic addition. It is organized based on the nature of initial radicals including C-, N-, O-, P-, S-centered and perfluoroalkyl (Rf) radicals. Reactions in- radicals including C-, N-, O-, P-, S-centered and perfluoroalkyl (Rf) radicals. Reactions involvingvolving electrophilic electrophilic addition addition (Scheme (Scheme1II-A), 1II-A), radical-radical radical-radical coupling coupling such as atomsuch trans-as atom trans- ferfer radical radical addition addition (ATRA) (ATRA) [19 ][19] or metal-catalyzed or metal-catalyzed coupling coupling (Scheme (Scheme1II-B )[20 1II-B)], radical [20], radical cyclizationcyclization for for ring ring formation formation (Scheme (Scheme1II-C) [ 211II-C)], and [21], cascade and reactions cascade [6 ]reactions involving more[6] involving thanmore two than steps two of radicalsteps of additions radical are additions not included are not in this included paper. Those in this type paper. of reactions Those type of mightreactions be the might topics be of the our topics future of review our future articles. review articles. I) Reactions covered in this paper Nu + - X Nu X ()n R (A) ()n R direct 1,2-difunctionalization . [O] X HO Ar R O + Ar addition X 1) ipso X OH (B) ()n R 2) [O] ()n Ar ()n R 1,2-difunctionalization via 1) HAT ipso rearrangement 2) [O] Nu Nu- X + X (C) ()n R ()n R distal difunctionalization II) Reactions not covered in this paper E - - X E X () R (A) n ()n R radical & electrophilic additions . [R] X Y addition X . + Y X ()n R (B) () R ()n R or met-cat n ATRA or cyclization metal-catalysis X X (C) Z R R ()n-1 ()n-1 Z radical addition & cycization SchemeScheme 1. 1.Radical-initiated Radical-initiated difunctionalization difunctionalization reactions. reactions. (I-A), I- directA, direct 1,2-difuctionalization. 1,2-difuctionalization. (I-B), I-B, 1,2-difuctionalization1,2-difuctionalization involving involvingipso ipso-reaction-reaction process. process. (I-C), I- distalC, distal difunctionalization. difunctionalization. (II-A ),II- 1,2-A, 1,2- difuctionalizationdifuctionalization involving involving electrophilic electrophilic addition. addition. (II-B ),II- atom-transferB, atom-transfer addition addition with orwith without or without metalmetal catalysis. catalysis. (II-C II-C),, reaction reaction involving involving cyclization. cyclization. 2. Carbon Radical-Initiated Reactions 2. Carbon Radical-Initiated Reactions Presented in this section are carbon radical-initiated reactions and C-, O-, and N- containingPresented moieties in arethis served section as are the carbon nucleophiles radical-initiated for the difunctionalizations. reactions and C-, The O-, initial and N-con- carbontaining radicals moieties could are served be generated as the nucleophiles by metal-containing for the SETdifunctionalizations. agents, using peroxides, The initial car- orbon under radicals photoredox could be conditions. generated Most by metal-cont alkenes usedaining for difunctionalization SET agents, using are peroxides, styrene or un- derivatives. Because addition of initial radicals to styrenes to form stabilized benzylic Molecules 2021, 26, 105 3 of 31 Molecules 2021, 26, 105
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