Recent advances in electrochemical copper catalysis for modern organic synthesis

• Yemin Kim and
• Won Jun Jang

Beilstein J. Org. Chem. 2025, 21, 155–178, doi:10.3762/bjoc.21.9

• bromine radical attack that leads to the formation of a cationic brominated copper complex 77. Anodic oxidation and subsequent proton transfer provide the desired product 73 and regenerate the copper catalyst. Olefin addition Hydrofunctionalization and difunctionalization of alkenes are valuable methods

Photoredox-catalyzed intramolecular nucleophilic amidation of alkenes with β-lactams

• Valentina Giraldi,
• Giandomenico Magagnano,
• Daria Giacomini,
• Pier Giorgio Cozzi and
• Andrea Gualandi

Beilstein J. Org. Chem. 2024, 20, 2461–2468, doi:10.3762/bjoc.20.210

• their investigation of the hydrofunctionalization reaction of unsaturated amides and thioamides [28]. They have found that the oxygen atom of the amide group, rather than the nitrogen atom, acted as a nucleophile, leading to the formation of 2-oxazolines and 2-thiazolines. Another recent example of

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• and silylation of styrenes catalyzed by NHC–CuOt-Bu to afford vinylboronates 168 and vinylsilanes 172 including trisubstituted derivatives, which are otherwise difficult to obtain through alkyne hydrofunctionalization. For the dehydrogenative borylation, two types of NHCs, 169 and 170, were employed

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• water then occurs releasing the final vinylcyclopropane product 126a and regenerating the active Rh(I) species. A later 2009 investigation revealed methyl groups α to the ester produced a hydrofunctionalization product [68]. Dienylboronate esters bearing methyl groups β to the ester group produced

Recent advances in the tandem annulation of 1,3-enynes to functionalized pyridine and pyrrole derivatives

• Yi Liu,
• Puying Luo,
• Yang Fu,
• Tianxin Hao,
• Xuan Liu,
• Qiuping Ding and
• Yiyuan Peng

Beilstein J. Org. Chem. 2021, 17, 2462–2476, doi:10.3762/bjoc.17.163

• necessary for this transformation. Recently, copper hydride (CuH) catalysis has been a wonderful procedure for olefin hydrofunctionalization via the formation of nucleophilic alkylcopper intermediate. In 2016, Buchwald and co-workers described a CuH-catalyzed asymmetric addition of olefin to ketones [65

Methodologies for the synthesis of quaternary carbon centers via hydroalkylation of unactivated olefins: twenty years of advances

• Thiago S. Silva and
• Fernando Coelho

Beilstein J. Org. Chem. 2021, 17, 1565–1590, doi:10.3762/bjoc.17.112

• hampered the development of more general catalytic hydrofunctionalization methodologies until Widenhoefer’s work in 2001 [25]. Based on previous works that had demonstrated the addition of stabilized carbanions [26][27] and enol silyl ethers [28] to olefins under stoichiometric Pd catalysis, the authors

• atom transfer Since the mid-2000s and mainly in the present decade, olefin hydrofunctionalization via metal hydride hydrogen atom transfer (MHAT) has gained increasing attention as a powerful tool for the functionalization of non-activated alkenes [48][49][50][51][52][53][54]. MHAT involves the

• of the potential of ATR in olefin hydrofunctionalization is the methodology developed by the Liu group [119], in which a carbon-centered radical is generated from simple alkanes instead of the more usual halogenated compounds. The authors reported that, in the presence of dicumyl peroxide (DCP) as a

Photocatalysis with organic dyes: facile access to reactive intermediates for synthesis

• Stephanie G. E. Amos,
• Marion Garreau,
• Luca Buzzetti and
• Jerome Waser

Beilstein J. Org. Chem. 2020, 16, 1163–1187, doi:10.3762/bjoc.16.103

• radical anions or their equivalents with other heteroatoms. However, organophotocatalysts have been only rarely used for this type of reduction. C2-charged radical species Since 2013, the Nicewicz group has developed a multitude of methodologies for the anti-Markovnikov hydrofunctionalization of alkenes

Recent advances in Cu-catalyzed C(sp³)–Si and C(sp³)–B bond formation

• Balaram S. Takale,
• Ruchita R. Thakore,
• Elham Etemadi-Davan and
• Bruce H. Lipshutz

Beilstein J. Org. Chem. 2020, 16, 691–737, doi:10.3762/bjoc.16.67

• the details of the mechanism for the hydrofunctionalization of internal alkenes and vinyl arenes (Scheme 55) [100]. Unlike acyclic alkenes, Tortosa et al. utilized cyclobutenes as well as bicyclic cyclobutenes as educts using (R)-DM-Segphos for Cu-catalyzed enantioselective borylation, affording

Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer

• Xiaoshen Ma and
• Seth B. Herzon

Beilstein J. Org. Chem. 2018, 14, 2259–2265, doi:10.3762/bjoc.14.201

• -butyl hydroperoxide (TBHP), and triethylsilane (Et3SiH) constitute an inexpensive, general, and practical reagent combination to initiate a broad range of Markovnikov-selective alkene hydrofunctionalization reactions. These transformations are believed to proceed by cobalt-mediated hydrogen atom

• reagent combination suggests it as a useful starting point to develop HAT reactions in complex settings. Keywords: HAT; hydrogen atom transfer; hydrofunctionalization; Introduction Many powerful methods to effect alkene hydrogenation [1][2][3][4] and Markovnikov-selective hydroheterofunctionalization (H

• ligand architectures [21], and often need to be prepared by multistep sequences. Here we report a uniform set of reaction conditions to achieve a broad range of HAT hydrofunctionalization reactions using the simple reagents cobalt acetoacetonate [Co(acac)2], tert-butyl hydroperoxide (TBHP), and

Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

• Martin Weiser,
• Sergej Hermann,
• Alexander Penner and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2015, 11, 568–575, doi:10.3762/bjoc.11.62

• et al. published the hydrofunctionalization of alkenes to the anti-Markovnikov products by photoredox catalysis using 9-mesityl-10-methylacridinium [20][21]. Herein, we want to present our complementary approach to perform inter- and intramolecular nucleophilic additions of alcohols to styrene