A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

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

A complementary approach to conjugated N-acyliminium formation through photoredox-catalyzed intermolecular radical addition to allenamides and allencarbamates

• Olusesan K. Koleoso,
• Matthew Turner,
• Felix Plasser and
• Marc C. Kimber

Beilstein J. Org. Chem. 2020, 16, 1983–1990, doi:10.3762/bjoc.16.165

• subsequent oxidation. We have established that the conjugated N-acyliminium intermediate can be formed from a broad range of allenamide precursors; additionally, the conjugated N-acyliminium intermediate can undergo nucleophilic addition with an arylamine or alcohol nucleophiles at the α- or γ-position, with

β-Hydroxy sulfides and their syntheses

• Mokgethwa B. Marakalala,
• Edwin M. Mmutlane and
• Henok H. Kinfe

Beilstein J. Org. Chem. 2018, 14, 1668–1692, doi:10.3762/bjoc.14.143

• enantioselectivities (Scheme 14) [44]. The reaction was also found to be compatible with aromatic N-heterocycles and alcohol nucleophiles to afford the corresponding products in moderate to good yields with high to excellent enantioselectivities [44]. The use of water as a solvent by Kobayashi and co-workers is

Acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with alcohols

• Katrina Tait,
• Alysia Horvath,
• Nicolas Blanchard and
• William Tam

Beilstein J. Org. Chem. 2017, 13, 2888–2894, doi:10.3762/bjoc.13.281

• Becquerel, 67087 Strasbourg, France 10.3762/bjoc.13.281 Abstract The acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicylic alkene using alcohol nucleophiles were investigated. Although this acid-catalyzed ring-opening reaction did not cleave the cyclopropane unit as planned, this

• reactions. The scope of the reaction was successfully expanded to include primary, secondary, and tertiary alcohol nucleophiles. Through X-ray crystallography, the stereochemistry of the product was determined which confirmed an SN2-like mechanism to form the ring-opened product. Keywords: acid catalysis

• ; alcohol nucleophiles; cyclopropanation; heterobicyclic compounds; ring-opening reactions; Introduction Heterobicyclic alkenes are useful templates to generate complex cyclic and acyclic systems [1][2]. 3-Aza-2-oxabicyclic alkenes are particularly interesting due to their asymmetric nature and the ability

Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene with alcohols

• Katrina Tait,
• Oday Alrifai,
• Rebecca Boutin,
• Jamie Haner and
• William Tam

Beilstein J. Org. Chem. 2016, 12, 2189–2196, doi:10.3762/bjoc.12.209

• cyclopropanated 7-oxabenzonorbornadiene derivatives using alcohol nucleophiles were investigated. The optimal conditions were found to be 10 mol % PdCl2(CH3CN)2 in methanol, offering yields up to 92%. The reaction was successful using primary, secondary and tertiary alcohol nucleophiles and was compatible with a

• variety of substituents on cyclopropanated oxabenzonorbornadiene. With unsymmetrical C1-substituted cyclopropanated 7-oxabenzonorbornadienes, the regioselectivity of the reaction was excellent, forming only one regioisomer in all cases. Keywords: alcohol nucleophiles; C1 substitution; cyclopropanated

• heteroatomic nucleophiles [23][24], or when ruthenium catalysts are used with alcohol nucleophiles [25]. Furthermore, unsubstituted dihydronaphthalenols 7 can be obtained through the reductive ring opening of oxabicyclic alkene 1 with hydride nucleophiles [26]. These intermediates find synthetic uses in the

Synthesis and ring openings of cinnamate-derived N-unfunctionalised aziridines

• Alan Armstrong and
• Alexandra Ferguson

Beilstein J. Org. Chem. 2012, 8, 1747–1752, doi:10.3762/bjoc.8.199

• camphorsulfonic acid (CSA), provides a facile synthesis of 1,2-aminoalcohols. The alcohol nucleophiles were used as solvents, as stoichiometric quantities resulted in decreased conversions. Single ring-opened products were observed in the 1H NMR spectra of the crude products in all cases. In MeOH, amino-acid

Cyclization of 5-hexynoic acid to 3-alkoxy-2-cyclohexenones

• Anne T. Hylden,
• Eric J. Uzelac,
• Zeljko Ostojic,
• Ting-Ting Wu,
• Keely L. Sacry,
• Krista L. Sacry,
• Lin Xi and
• T. Nicholas Jones

Beilstein J. Org. Chem. 2011, 7, 1323–1326, doi:10.3762/bjoc.7.155

• -alkoxy-2-cyclohexenones proceeds in good yields (58–90%). 3-Hexynoic acid was converted to its acyl chloride with the aid of oxalyl chloride and was cyclized to 3-chloro-2-cyclohexenone upon addition of indium(III) chloride. Subsequent addition of alcohol nucleophiles led to the desired 3-alkoxy-2

• formed from esterification of unreacted oxalyl chloride with excess alcohol nucleophiles, and thus a basic hydrolysis step was added to our work-up procedure. Secondary alcohols required heating to 90 °C following addition of the alcohol nucleophile to promote product formation. IR and NMR spectral data

• prepared directly in 78% yield under our cyclization conditions except that the addition of an alcohol nucleophile was omitted (Scheme 2). Based on the isolation of 4 and the apparent steric influence of the alcohol nucleophiles, as observed in the yield data in Table 2, we have proposed a possible pathway

Recent advances in the gold-catalyzed additions to C–C multiple bonds

• He Huang,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103

• benzobicyclo[5.3.1]acetals 87 were produced when triazole–gold was employed as the catalyst. With alcohol nucleophiles, gold(I)-catalyzed cyclization of o-alkynyl benzaldehyde 88 and benzaldimine–chromium complexes gave stereoselectively 1-anti-functionalized heterocycle chromium complexes 89 (Scheme 16) [47

Carbasugar analogues of galactofuranosides: α-O-linked derivatives

• Jens Frigell and
• Ian Cumpstey

Beilstein J. Org. Chem. 2010, 6, 1127–1131, doi:10.3762/bjoc.6.129

• Using an indirect method, we have synthesised α-linked carbasugar analogues of galactofuranosides for the first time. Ring opening of a β-talo configured carbasugar 1,2-epoxide by alcohol nucleophiles under Lewis acidic conditions proceeded with very good regioselectivity to give α-talo configured C1

• what appears to be a general route towards carbasugar analogues of β-galactofuranosides [9]. In our approach, alcohol nucleophiles attack an α-galacto carbasugar 1,2-epoxide 1 (Figure 1) under Lewis acidic conditions with excellent regioselectivity for attack at C1. The regioselectivity may be

• (favoured sterically and electronically) leads to stereoelectronically unfavourable [11] 1,2-trans-diequatorial opening. This nucleophilic dilemma presumably accounts for the poor regioselectivity and yields of such reactions. With alcohol nucleophiles, no coupling products were observed with either α-gluco