Electrochemical reduction of unsaturated carbon–carbon bonds via 3d transition-metal catalysis

• Geon Kang,
• Minki Jeon,
• Pooja Kumari Jat,
• Cheoljae Kim and
• Isaac Choi

Beilstein J. Org. Chem. 2026, 22, 955–981, doi:10.3762/bjoc.22.75

• unsaturated C–C bonds, enabling precise control without molecular hydrogen or stoichiometric reductants. This review summarizes recent advances in iron-, cobalt-, and nickel-catalyzed electroreduction of alkynes and alkenes, highlighting how electrochemical parameters and catalyst design unlock distinct

• ; electroorganic synthesis; reaction mechanism; 3d transition metals; unsaturated C–C bonds; Introduction Reductions of unsaturated C–C bonds Reduction of unsaturated C–C bonds, most notably, alkynes and alkenes, is a synthetic method that has been widely and extensively discussed with a long and rich history

• a divided cell. Modes for the reduction of C–C bonds Electrochemical reduction of unsaturated C–C bonds is dictated by the mode of electron and proton delivery, and the identity of the metal catalyst or redox mediator (Figure 2). Within this framework, the underlying mechanistic modes for the

Radical ligand transfer: a general strategy for radical functionalization

• David T. Nemoto Jr,
• Kang-Jie Bian,
• Shih-Chieh Kao and
• Julian G. West

Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90

• elimination-like pathway to afford unsaturated C–C bonds in the presence of copper(II) sulfate, presumably via competitive RPC to the carbocation followed by E1 olefination. Kochi also demonstrated that RLT can be combined with other radical generation strategies to enable new, non-biomimetic reactions to be

Highly regio- and stereoselective phosphinylphosphination of terminal alkynes with tetraphenyldiphosphine monoxide under radical conditions

• Dat Phuc Tran,
• Yuki Sato,
• Yuki Yamamoto,
• Shin-ichi Kawaguchi,
• Shintaro Kodama,
• Akihiro Nomoto and
• Akiya Ogawa

Beilstein J. Org. Chem. 2021, 17, 866–872, doi:10.3762/bjoc.17.72

• (X)PPh2 to unsaturated C–C bonds. The addition of Ph2P(O)PPh2 (1) to 1-octyne (2a). Phosphinylphosphination of various terminal alkynes 2 with 1. aIsolated yields. V-40 = 1,1’-azobis(cyclohexane-1-carbonitrile). bRepeated 2 times. Attempted radical addition to internal alkynes and insight into the

Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups

• Cyrus Mowdawalla,
• Faiz Ahmed,
• Tian Li,
• Kiet Pham,
• Loma Dave,
• Grace Kim and
• I. F. Dempsey Hyatt

Beilstein J. Org. Chem. 2018, 14, 1039–1045, doi:10.3762/bjoc.14.91

• transmetallation with an appropriate metalloid substrate. This concept is counter to previous mechanisms in which the electrophilic hypervalent iodine reagent is attacked by unsaturated C–C bonds [18][19][20][21][22]. To show evidence for this transmetallation event, benzyl metalloid groups were used under the

Continuous formation of N-chloro-N,N-dialkylamine solutions in well-mixed meso-scale flow reactors

• A. John Blacker and
• Katherine E. Jolley

Beilstein J. Org. Chem. 2015, 11, 2408–2417, doi:10.3762/bjoc.11.262

• -Chloramines provide a versatile and reactive class of reagents for use in electrophilic amination and other reactions. N-Chloro-N,N-dialkylamines have been shown to offer a broad range of products from reactions with i) unsaturated C–C bonds to give amines [1][2][3] and heterocycles [1][4]; ii) Grignard and

Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

• Hideki Yorimitsu

Beilstein J. Org. Chem. 2013, 9, 1269–1277, doi:10.3762/bjoc.9.143

• . This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides. Keywords: addition; free radical; homolysis; phosphine; radical; substitution; Introduction Organophosphorus compounds constitute an important class of

• literature [19][20][21]. This review deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides. Review Radical addition of phosphination agents Stannylphosphines of the type R3Sn–PR’2 are known to undergo radical addition to carbon

Efficient gold(I)/silver(I)-cocatalyzed cascade intermolecular N-Michael addition/intramolecular hydroalkylation of unactivated alkenes with α-ketones

• Ya-Ping Xiao,
• Xin-Yuan Liu and
• Chi-Ming Che

Beilstein J. Org. Chem. 2011, 7, 1100–1107, doi:10.3762/bjoc.7.126

• acid to activate unsaturated C–C bonds towards nucleophilic attack [1][2][3][4][5][6][7][8][9][10] (for selected reviews on gold-catalyzed reactions see [1][2][3][4][5][6][7][8][9]). Based on this mode of activation, several methods for the gold-catalyzed inter- and intramolecular addition of oxygen

Gold-catalyzed oxidation of arylallenes: Synthesis of quinoxalines and benzimidazoles

• Dong-Mei Cui,
• Dan-Wen Zhuang,
• Ying Chen and
• Chen Zhang

Beilstein J. Org. Chem. 2011, 7, 860–865, doi:10.3762/bjoc.7.98

• ; oxidation; quinoxaline; Introduction Recently, several research groups have developed gold-catalyzed homogeneous catalytic reactions [1]. A variety of organic transformations have been shown to be mediated by gold(I) or gold(III) complexes in solution. In addition to its ability to activate unsaturated C–C

• bonds, the catalysis of nucleophilic addition by gold complexes for the formation of carbon–carbon and carbon–heteroatom bonds has been one of the most investigated reactions in recent organometallic catalysis [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]. In

Continuous flow hydrogenation using polysilane-supported palladium/alumina hybrid catalysts

• Hidekazu Oyamada,
• Takeshi Naito and
• Shū Kobayashi

Beilstein J. Org. Chem. 2011, 7, 735–739, doi:10.3762/bjoc.7.83

• palladium/alumina (Pd/(PSi–Al2O3)) hybrid catalysts were developed. Our original Pd/(PSi–Al2O3) catalysts were used successfully in these systems and the hydrogenation of unsaturated C–C bonds and a nitro group, deprotection of a carbobenzyloxy (Cbz) group, and a dehalogenation reaction proceeded smoothly

• ., the reduction of unsaturated C–C bonds and a nitro group, deprotection of a Cbz group, and a dehalogenation reaction, all proceeded smoothly. The catalysts could be used for a long time, with high activity being retained for at least 8 h under neat conditions. It is noted that in all cases no Pd