Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer

• Mohd Farhan Ansari,
• Atul Kumar Maurya,
• Abhishek Kumar and
• Saravanakumar Elangovan

Beilstein J. Org. Chem. 2024, 20, 1111–1166, doi:10.3762/bjoc.20.98

• reactions allow the sustainable construction of C–C and C–N bonds using alcohols as hydrogen donors. In recent years, manganese complexes have been explored as efficient catalysts in these reactions. This review highlights the significant progress made in manganese-catalyzed C–C and C–N bond-formation

• reactions via hydrogen auto-transfer, emphasizing the importance of this methodology and manganese catalysts in sustainable synthesis strategies. Keywords: alcohols; alkylation; amines; borrowing hydrogen; hydrogen auto-transfer; manganese; Introduction The construction of C–C and C–N bonds is of utmost

• friendly and atom-economical process for C–C and C–N bond formations utilizing alcohol as an alkylating agent and hydrogen donor, producing water as the only side-product [6][7][8][9]. Notably, alcohols are inexpensive, abundant and can be obtained from biomass, which makes this method even more attractive

Carbonylative synthesis and functionalization of indoles

• Alex De Salvo,
• Raffaella Mancuso and
• Xiao-Feng Wu

Beilstein J. Org. Chem. 2024, 20, 973–1000, doi:10.3762/bjoc.20.87

• ) and the corresponding urea derivatives as byproducts. In the middle of the same year, Wu’s group succeeded in using N-(2-bromobenzoyl)indoles in the reaction with alcohols and anilines to achieve a Pd-catalyzed diasteroselective carbonylative cyclodearomatization [62]. The synthesis proceeded best

• when the reaction was performed in the presence of 10 mol % of Pd(OAc)2 and dppp as catalyst system, Na2WO4∙2H2O (1 or 2 equiv) as base and an excess of nucleophile (alcohols or anilines) in toluene as reaction solvent under 5 bar of CO at 100 °C. Also, 20 mol % of LiBr were added as additive when

• alcohols were used as the nucleophiles (Scheme 32). About three years later, the same group developed a simple and efficient method to access CO-linked heterocyclic scaffolds by a Pd-catalyzed carbonylative cyclization of alkene–indole derivatives with 2-alkynylanilines and 2-alkynylphenols, in the

Innovative synthesis of drug-like molecules using tetrazole as core building blocks

• Jingyao Li,
• Ajay L. Chandgude,
• Qiang Zheng and
• Alexander Dömling

Beilstein J. Org. Chem. 2024, 20, 950–958, doi:10.3762/bjoc.20.85

• Passerini-tetrazole product. Then, the Swern oxidation [22][23][24], which is widely exploited and has a wide tolerance of functional groups, was used to convert the tetrazole containing alcohols to aldehydes, in particular for derivatives bearing convertible isocyanides. Most building blocks were well

Direct synthesis of acyl fluorides from carboxylic acids using benzothiazolium reagents

• Lilian M. Maas,
• Alex Haswell,
• Rory Hughes and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2024, 20, 921–930, doi:10.3762/bjoc.20.82

• developed a series of 2-(fluoroalkylthio)benzothiazolium (BT-SRF) reagents for the deoxygenative transfer of SRF (RF = poly- or perfluoroalkyl) groups into organic molecules (Figure 1). In an initial report, the trifluoromethylthio-containing salt, BT-SCF3, was reacted with unactivated aliphatic alcohols to

Three-component N-alkenylation of azoles with alkynes and iodine(III) electrophile: synthesis of multisubstituted N-vinylazoles

• Jun Kikuchi,
• Roi Nakajima and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2024, 20, 891–897, doi:10.3762/bjoc.20.79

• difunctionalization of alkynes with various heteroatom and carbon nucleophiles [27][28][29][30][31][32][33][34]. Specifically, intermolecular trans-iodo(III)functionalization of alkynes has been achieved using oxygen nucleophiles such as alcohols [28][32], ethers [33], carboxylic acids [31], phosphate esters [31

(Bio)isosteres of ortho- and meta-substituted benzenes

• H. Erik Diepers and
• Johannes C. L. Walker

Beilstein J. Org. Chem. 2024, 20, 859–890, doi:10.3762/bjoc.20.78

• distances d and scaffold carbon distances r are only slightly smaller than for the corresponding meta-benzenes. At the same time, the substituent angle φ1 is about 30° larger in 2-oxa-1,4-BCH. Mykhailiuk and co-workers could synthesise the 2-oxa-1,4-BCHs 110a–f in high yields by iodocyclisation of alcohols

• 109 (Scheme 12A) [58]. The formed products all contained a pendant primary iodide group and the synthesis was additionally shown to be tolerant of functional groups including protected amines (in 110c), protected alcohols (in 110d) and nitriles (in 110e). Grygorenko and co-workers accessed fluorine

• could also be oxidised to acid 112, from which redox active ester 118 could be accessed. An alternative approach to 2-oxa-1,4-BCHs involves the C–H-borylation of monosubstituted 2-oxa-BCHs developed by Hartwig and co-workers (Scheme 12C) [57]. Functional groups including halides (in 120b), alcohols (in

Skeletal rearrangement of 6,8-dioxabicyclo[3.2.1]octan-4-ols promoted by thionyl chloride or Appel conditions

• Martyn Jevric,
• Julian Klepp,
• Johannes Puschnig,
• Oscar Lamb,
• Christopher J. Sumby and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2024, 20, 823–829, doi:10.3762/bjoc.20.74

• 10.3762/bjoc.20.74 Abstract A skeletal rearrangement of a series of 6,8-dioxabicyclo[3.2.1]octan-4-ols has been developed using SOCl2 in the presence of pyridine. An oxygen migration from C5 to C4 was observed when the C4 alcohols were treated with SOCl2/pyridine, giving a 2-chloro-3,8-dioxabicyclo[3.2.1

• ]octane ring-system via the chlorosulfite intermediate. Analogous allylic alcohols with endocyclic and exocyclic unsaturations underwent chlorination without rearrangement due to formation of allylic cations. The rearrangement was also demonstrated using Appel conditions, which gave similar results via

• , although 11a was sufficiently stable for filtration through a pad of silica. Applying these conditions and isolation protocols to all 3,3-disubstituted alcohols 10c–f gave moderate to excellent yields of the rearrangement products 11c–f as single stereoisomers. The reactions of alcohols 10b,d,e also gave

Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• employing two protocols (Scheme 23A). Generally, protocol A works well for the synthesis of tertiary chlorides, whereas protocol B is preferable for the synthesis of secondary chlorides (Scheme 23B). Surprisingly, free alcohols required protection even though the reaction is carried out in ethanol as a

• activated alkenes [86]. Subjecting citronellol (122) to the optimized reaction conditions resulted in the formation of chloride 133 with a yield of 62% (Scheme 25). It is worth noting that the iron-catalyzed procedure tolerates free alcohols, a distinction from Carreira's protocol [80]. In 2014, the Thomas

• conclusion we wish to point out that this reaction provides a convenient procedure to achieve anti Markovnikov addition of alcohols to olefins which can presumably be extended to other systems. Furthermore, the addition of other nucleophiles to photochemically generated cation radicals would make this type

Synthesis of new representatives of A₃B-type carboranylporphyrins based on meso-tetra(pentafluorophenyl)porphyrin transformations

• Victoria M. Alpatova,
• Evgeny G. Rys,
• Elena G. Kononova and
• Valentina A. Ol'shevskaya

Beilstein J. Org. Chem. 2024, 20, 767–776, doi:10.3762/bjoc.20.70

• biomolecules via the nucleophilic aromatic (SNAr) substitution reactions [15][16]. A variety of nucleophiles such as amines [17][18], alcohols [18][19][20], thiols [17][19][21][22][23], and carboranes [17][24][25][26][27] have been studied in selective SNAr substitution reactions of the p-fluorine atoms in

Chemoenzymatic synthesis of macrocyclic peptides and polyketides via thioesterase-catalyzed macrocyclization

• Senze Qiao,
• Zhongyu Cheng and
• Fuzhuo Li

Beilstein J. Org. Chem. 2024, 20, 721–733, doi:10.3762/bjoc.20.66

• polyketides or peptides, and form an ester bond. Then, they catalyze either intramolecular macrocyclization to give macrolactones or macrolactams with attacking of internal nucleophiles (alcohols or amine), or hydrolysis to release linear acids or peptides (Scheme 1b). Although TE domains may display

SOMOphilic alkyne vs radical-polar crossover approaches: The full story of the azido-alkynylation of alkenes

• Julien Borrel and
• Jerome Waser

Beilstein J. Org. Chem. 2024, 20, 701–713, doi:10.3762/bjoc.20.64

• , entry 10). The addition of DABCO [18] or TBAI [50], two additives known to activate azidobenziodoxolone (ABX), afforded complex mixtures with no trace of 4a (Table 1, entry 11). Acids or fluorinated alcohols were tested to activate the different hypervalent iodine reagents. While AcOH, TFA and TFE had

Palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines

• Geng-Xin Liu,
• Xiao-Ting Jie,
• Ge-Jun Niu,
• Li-Sheng Yang,
• Xing-Lin Li,
• Jian Luo and
• Wen-Hao Hu

Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59

• products 4a and 6a (Scheme 6). Both model reactions with diene 2a and allene 5a were proven to be easily scalable without further conditions optimization, delivering unsaturated γ- and ε-AA derivatives 4a and 6a in good yields. Starting from the unsaturated ε-AA derivative 4a, unsaturated ζ-amino alcohols

Entry to new spiroheterocycles via tandem Rh(II)-catalyzed O–H insertion/base-promoted cyclization involving diazoarylidene succinimides

• Alexander Yanovich,
• Anastasia Vepreva,
• Ksenia Malkova,
• Grigory Kantin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2024, 20, 561–569, doi:10.3762/bjoc.20.48

• alcohols, followed by base-promoted cyclization to afford the target spirocyclic compounds in good to high yields. Keywords: diazoarylidene succinimides; intramolecular cyclization; rhodium(II) carbene O–H insertion; spirocycles; Introduction Spirocyclic motifs have emerged as auspicious frameworks for

• from each of the bromo-substituted alcohols used by us have two main pathways of transformation under the action of base: 1) exo-tet cyclization with substitution of the bromine atom and formation of the spirocycle, and 2) migration of the exocyclic double C=C bond into the imide cycle (the process is

Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• Since the seminal 1998 report by Teles et al. on the gold(I)-catalyzed addition of alcohols to alkynes [1], a multitude of gold-catalyzed reactions have been reported. Great successes in mechanistic analysis and synthetic methods have been achieved for allene and alkyne activation, while the activation

• effect of MeOH co-solvent on the 1a → 3a transformation was due to its role as a hydrogen bonding donor (proton source), or due to its role as a hydrogen bonding acceptor (Lewis base) [44]. To this end, we examined the impact of different alcohols (varied acidity and polarity) and different non-protic

• Lewis bases as additive to the bulk CH2Cl2 solvent (Figure 6) and compared them to the baseline rate in the absence of additive. The rates of formation of 3a are mildly sensitive to alcohol structure with MeOH outperforming EtOH and propanol. For the set of linear alcohols, the shorter the chain, the

Nucleophilic functionalization of thianthrenium salts under basic conditions

• Xinting Fan,
• Duo Zhang,
• Xiangchuan Xiu,
• Bin Xu,
• Yu Yuan,
• Feng Chen and
• Pan Gao

Beilstein J. Org. Chem. 2024, 20, 257–263, doi:10.3762/bjoc.20.26

• -metal-catalyzed cross-coupling [32][33] and aminofunctionalization [34] of alkenes were achieved, benefiting from the unique reactivity of organothianthrenium species that are generated through the reaction of alkenes and thianthrene sulfoxide (TT=O) or thianthrene (TT) (Scheme 1b). Alcohols are widely

• [35], it is still a great challenge to transform alcohols into valuable chemicals [36][37][38]. A recent study by Shi and co-workers has successfully converted alcohols into thianthrenium salts, enabling the transformation of the hydroxy (OH) group into various functional groups via the photoassisted

A series of perylene diimide cathode interlayer materials for green solvent processing in conventional organic photovoltaics

• Kathryn M. Wolfe,
• Shahidul Alam,
• Eva German,
• Fahad N. Alduayji,
• Maryam Alqurashi,
• Frédéric Laquai and
• Gregory C. Welch

Beilstein J. Org. Chem. 2023, 19, 1620–1629, doi:10.3762/bjoc.19.119

• impact of morphological changes on device performance [18][19]. With respect to the latter, we have introduced ethyl acetate as a suitable green solvent to process CILs onto high performance BHJs (e.g., PM6:Y6). Most CILs have been processed from alcohols as to not damage the underlying hydrophobic BHJ

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• of surfactants, which are also called emulsifiers within the first few minutes [26]. Emulsifiers such as sodium lauryl sulfate, sodium or potassium salts of fatty acids (soaps), salts of alkylbenzene sulfonates, and O-polyoxyethyleneated long-chain alcohols are used to change the two incompatible

Complexes of resorcin[4]arene with secondary amines: synthesis, solvent influence on “in-out” structure, and theoretical calculations of non-covalent interactions

• Waldemar Iwanek

Beilstein J. Org. Chem. 2023, 19, 1525–1536, doi:10.3762/bjoc.19.109

• ], amino alcohols [10], and amino acids [11] have been studied due to their potential applications in supramolecular chemistry, drug delivery, and molecular recognition. The complexation of R[4]A with amines is based on the formation of hydrogen bonds between the hydroxy groups of the resorcinol units and

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• ]. Moreover, sulfenylation of ketoximes and secondary nitro compounds toward N-arenesulfenyl ketimines occurred by applying N-(phenylthio)phthalimide [69]. In 2011, Shi et al. developed a method for the sulfenylation of unsaturated alcohols 86 by N-(benzylthio)succinimide 1 access to tetrahydrofurans 87 and

• presence of TMSOTf. Catalyst-free sulfenylation by N-(sulfenyl)succinimides/phthalimides In 2015, oxysulfenylation of styrene derivatives 9 utilizing 1-(arylthio)pyrrolidine-2,5-diones 1 and alkyl/benzyl alcohols 86 toward β-alkoxy sulfides was developed by Fu et al. (Scheme 65) [95]. In this metal-free

• of the product, while benzoyl peroxide (BPO) gave a low yield. Various nucleophiles 161, including ammonia, alkylamines, hydrazines, alcohols and alkoxides, indole, N-alkylpyrrole, N-substituted anilines, PhSH, and PhMgBr worked well under these conditions. Asymmetric thiolation of 4-substituted

Functions of enzyme domains in 2-methylisoborneol biosynthesis and enzymatic synthesis of non-natural analogs

• Binbin Gu,
• Lin-Fu Liang and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 1452–1459, doi:10.3762/bjoc.19.104

• obtained through standard phosphorylation of the corresponding known alcohols [35][36][37]. In a first screening, these derivatives were tested in all possible combinations in small scale reactions (0.3 mg of each substrate) with FPPS. The results were investigated through dephosphorylation with calf

α-(Aminomethyl)acrylates as acceptors in radical–polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping

• Angel Palillero-Cisneros,
• Paola G. Gordillo-Guerra,
• Fernando García-Alvarez,
• Olivier Jackowski,
• Franck Ferreira,
• Fabrice Chemla,
• Joel L. Terán and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2023, 19, 1443–1451, doi:10.3762/bjoc.19.103

• stereocenter. α-(Aminomethyl)acrylates 5–7 reacted smoothly at −33 °C within 2 h with Et2Zn in the presence of cyclohexanone to afford amino alcohols 18–20 in quite good yields (63–68%). Even better yields were obtained with enoates 8a and 8b both with cyclohexanone and acetone as carbonyl partners. Starting

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

• of the NHC–CuCl-catalyzed hydroborylation of propargylic alcohols (157, R = H) and ethers (157, R = aryl, alkyl) was dependent on the size of the NHC [85] (Scheme 62). Interestingly, the application of the catalyst 158 comprising a bulkier NHC preponderantly led to the sterically crowded α

Functional characterisation of twelve terpene synthases from actinobacteria

• Anuj K. Chhalodia,
• Houchao Xu,
• Georges B. Tabekoueng,
• Binbin Gu,
• Kizerbo A. Taizoumbe,
• Lukas Lauterbach and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 1386–1398, doi:10.3762/bjoc.19.100

• ; biosynthesis; enzymes; NMR spectroscopy; terpenes; Introduction Terpene synthases are remarkable enzymes that can convert acyclic and achiral oligoprenyl pyrophosphates into terpene hydrocarbons or alcohols of high structural complexity. These enzymatic reactions are initiated by ionisation of the substrate

• in sesquiterpene biosynthesis that can be reactivated by reprotonation for a second cyclisation to eudesmane (6,6-bicyclic) or guaiane (7,5-bicyclic) sesquiterpene hydrocarbons or alcohols, respectively [46][47]. Starting from 26, such a protonation induced cyclisation can lead to C that is the

Visible-light-induced nickel-catalyzed α-hydroxytrifluoroethylation of alkyl carboxylic acids: Access to trifluoromethyl alkyl acyloins

• Feng Chen,
• Xiu-Hua Xu,
• Zeng-Hao Chen,
• Yue Chen and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98

• nickel-catalyzed coupling of aryl bromides with an α-hydroxytrifluoroethyl radical for the synthesis of trifluoromethyl aryl alcohols [39]. Encouraged by this work, we envisioned that the nickel-catalyzed coupling of carboxylic acids-derived acyl electrophiles with an α-hydroxytrifluoroethyl radical

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

• protection was not regioselective (a mixture of primary and secondary protected alcohols was formed). The acylation of the secondary alcohol was then achieved with acetic anhydride in the presence of pyridine. Then, the deprotection of the trityl moiety of compound 12.4 by catalytic hydrogenation failed