2-Heteroarylethylamines in medicinal chemistry: a review of 2-phenethylamine satellite chemical space

• Carlos Nieto,
• Alejandro Manchado,
• Ángel García-González,
• David Díez and
• Narciso M. Garrido

Beilstein J. Org. Chem. 2024, 20, 1880–1893, doi:10.3762/bjoc.20.163

• hydration reaction of carbon dioxide to bicarbonate, cyanates to carbamic acids, aldehydes to gem-diols, etc., and represent a potential therapeutic target for diseases like osteoporosis, edema, obesity or cancer [29]. Alım et al. [30] evaluated a series of thiophene sulfonamides based on the high stability

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

• formation of linked polyheterocycles 75. The authors then decided to perform the reaction using 3 equiv of aldehyde 70 under acidic conditions (Scheme 25, conditions a). The presence of a nucleophilic indole in the GBB adducts 71 induced further additions towards the excess aldehydes 70. The diols 73

Syntheses and medicinal chemistry of spiro heterocyclic steroids

• Laura L. Romero-Hernández,
• Ana Isabel Ahuja-Casarín,
• Penélope Merino-Montiel,
• Sara Montiel-Smith,
• José Luis Vega-Báez and
• Jesús Sandoval-Ramírez

Beilstein J. Org. Chem. 2024, 20, 1713–1745, doi:10.3762/bjoc.20.152

Ring opening of photogenerated azetidinols as a strategy for the synthesis of aminodioxolanes

• Henning Maag,
• Daniel J. Lemcke and
• Johannes M. Wahl

Beilstein J. Org. Chem. 2024, 20, 1671–1676, doi:10.3762/bjoc.20.148

• promising starting point for pursuing this ring-opening attempt [41]. We hypothesized that this approach would allow the synthesis of 3-amino-1,2-diols, a motif commonly found in pharmaceuticals such as, e.g., β-blockers [42]. Our envisioned one-pot protocol features protonation of the azetidine from

• in the synthesis of highly functionalized dioxolanes and 3-amino-1,2-diols. We believe that the concept of building and releasing strain energy, particularly when paired with photochemical means, is of general interest and its structural simplicity should allow for an expansion to other substrates

Stability trends in carbocation intermediates stemming from germacrene A and hedycaryol

• Naziha Tarannam,
• Prashant Kumar Gupta,
• Shani Zev and
• Dan Thomas Major

Beilstein J. Org. Chem. 2024, 20, 1189–1197, doi:10.3762/bjoc.20.101

• diols by addition of water. For each of these intermediates, simple deprotonation or nucleophilic attack by water are possible. Also, hydride shifts can occur first, which widens the chemical space of possible products. Additionally, the presence of multiple stereocenters adds to the rich

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

• ). The reaction proceeded via the dehydrogenation of the alcohol, aldol condensation, and hydrogenation of α,β-unsaturated ketones. In 2019, Leitner and his group introduced an outstanding cascade BH approach for the synthesis of various substituted cycloalkanes by coupling diols and secondary alcohols

• constructed by treating aromatic ketones with substituted diols. However, a stoichiometric amount of the base (4 equiv), excess of diols (4 equiv), and long reaction time (32 h) were required to deliver the desired products (Scheme 34). The proposed mechanism demonstrated that the active amido complex Mn1-a

• intramolecular BH reaction for the formation of cycloalkanes from ketones and 1,n-diols [66]. Different substituted 1,5-diols were coupled with 1-(2,3,4,5,6-pentamethylphenyl)ethan-1-one using 4 mol % of catalyst Mn13 and 2 equiv of t-BuOK as base in t-AmOH at 140 °C for 36 h to give 51–98% yield of the six

Discovery and biosynthesis of bacterial drimane-type sesquiterpenoids from Streptomyces clavuligerus

• Dongxu Zhang,
• Wenyu Du,
• Xingming Pan,
• Xiaoxu Lin,
• Fang-Ru Li,
• Qingling Wang,
• Qian Yang,
• Hui-Min Xu and
• Liao-Bin Dong

Beilstein J. Org. Chem. 2024, 20, 815–822, doi:10.3762/bjoc.20.73

• a precursor for derivatives 2–4. The biosynthetic pathway is likely to involve enzymatic modifications at the C-2 and C-3 positions, leading to the formation of diols 2 and 3, with additional oxidation steps producing ketone 4 (Figure 3b). This supports the presence of three P450s in the cav cluster

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions

• Matthias R. Steiner,
• Max Schmallegger,
• Larissa Donner,
• Johann A. Hlina,
• Christoph Marschner,
• Judith Baumgartner and
• Christian Slugovc

Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6

• synthesis of carbonates from CO2 [24][25][26] and the synthesis of oxazolidines from isocyanates and epoxides [27]. Furthermore, their application in primary hydroxy group selective acylation of diols [28] and their use as organophotoredox catalysts [29][30] is known. The latter mentioned catalysts are

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides

• Kan Tang,
• Megan R. Brown,
• Chad Risko,
• Melissa K. Gish,
• Garry Rumbles,
• Phuc H. Pham,
• Oana R. Luca,
• Stephen Barlow and
• Seth R. Marder

Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142

• [4][5], while other reducing species have been formed from in situ reactions of simple diols or diamines [13]. Another approach is to utilize dimers formed by highly reducing radicals, such the bibenzoimidazoles (Y-DMBI)2 (Figure 1c). (Me-DMBI)2 was first reported in 1984 and used as a reductant in

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

• important functional groups such as dicarbonyls [15], diols [16], amino ketones [17] and so on. Recently, the introduction of a trifluoromethyl group into organic molecules has received great attention due to their wide applicability in medicinal [18][19] and materials [20][21] chemistry. The toxicological

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

• was selectively alkylated on the primary alcohol to produce 20.2 via the use of dibutyltin oxide as selective reagent for the alkylation of diols [109]. For this reaction, CsF was added to increase the reactivity of the alkyl bromide, likely by a combined effect that includes the interaction of the

Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

• Cécile Alleman,
• Charlène Gadais,
• Laurent Legentil and
• François-Hugues Porée

Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• cyclization affording the final product. Similarly, the dioxygenation of vinylarenes by diols was realized affording 1,4-dioxaheterocycles [112] (Scheme 21B). Triarylimidazoles have found similar applications as mediators for electrochemical oxidations [113] (Scheme 22). The reaction was suggested to proceed

Electrochemical formal homocoupling of sec-alcohols

• Kosuke Yamamoto,
• Kazuhisa Arita,
• Masashi Shiota,
• Masami Kuriyama and
• Osamu Onomura

Beilstein J. Org. Chem. 2022, 18, 1062–1069, doi:10.3762/bjoc.18.108

• anode-free electrochemical protocol for the synthesis of pinacol-type vic-1,2-diols from sec-alcohols, namely benzyl alcohol derivatives and ethyl lactate. The corresponding vic-1,2-diols are obtained in moderate to good yields, and good to high levels of stereoselectivity are observed for sec-benzyl

• -valent metal reductants, such as Al, Ti, V, Zn, and Sm (Scheme 1a). Although these protocols have proven to be a reliable strategy to access vic-1,2-diols, producing a large amount of metal waste may be a major drawback especially in a large-scale synthesis. Thus, the improved procedures using a

• ][16][17][18]. In addition to the reductive coupling of carbonyl compounds, oxidative homocoupling reactions of benzyl alcohols under transition metal- or semiconductor-based photoredox catalysis have been demonstrated as attractive approaches to access vic-1,2-diols [19][20][21][22][23

A study of the photochemical behavior of terarylenes containing allomaltol and pyrazole fragments

• Constantine V. Milyutin,
• Andrey N. Komogortsev,
• Boris V. Lichitsky and
• Valeriya G. Melekhina

Beilstein J. Org. Chem. 2022, 18, 588–596, doi:10.3762/bjoc.18.61

• -hydroxy-1,2-diketones 2 is the condensation with 1,2-phenylenediamine resulting in the formation of fused quinoxalines 3 (Scheme 1A) [22]. Another variant of similar catching reaction is reduction by NaBH3CN with the formation of diols 4 (Scheme 1A) [23]. Thus, the introduction of additional reagents

BINOL as a chiral element in mechanically interlocked molecules

• Matthias Krajnc and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2022, 18, 508–523, doi:10.3762/bjoc.18.53

• desymmetrization of meso-1,2-diols [58]. The [2]rotaxane (R)-42 was synthesized by interaction of the ammonium salt 41 with the BINOL-based macrocycle (R)-12 and end-capping with 3,5-di-tert-butylbenzoic acid (see Figure 10). In the asymmetric desymmetrization reaction of meso-hydrobenzoin, rotaxane (R)-42 gave

• desymmetrization reaction of meso-1,2-diols with rotaxane (R)-42. Synthesis of Niemeyer´s axially chiral [2]catenane (S,S)-47. Results for the enantioselective transfer hydrogenation of 2-phenylquinoline with catalysts (S,S)-47, (S)-48, and (S)-49. Synthesis of Niemeyer´s chiral [2]rotaxanes (S)-56/57. Results for

Cs₂CO₃-Promoted reaction of tertiary bromopropargylic alcohols and phenols in DMF: a novel approach to α-phenoxyketones

• Ol'ga G. Volostnykh,
• Olesya A. Shemyakina,
• Anton V. Stepanov and
• Igor' A. Ushakov

Beilstein J. Org. Chem. 2022, 18, 420–428, doi:10.3762/bjoc.18.44

• building blocks for the production of other important molecules (e.g., amino alcohols, diols, etc.) [40][41][42][43][44][45][46] and potential pharmaceuticals. α-Hydroxyketones are structural subunits of natural products [47][48][49] and compounds possessing immunosuppressant [50], antidepressant [51

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

Highly stereocontrolled total synthesis of racemic codonopsinol B through isoxazolidine-4,5-diol vinylation

• Lukáš Ďurina,
• Anna Ďurinová,
• František Trejtnar,
• Ľuboš Janotka,
• Lucia Messingerová,
• Jana Doháňošová,
• Ján Moncol and
• Róbert Fischer

Beilstein J. Org. Chem. 2021, 17, 2781–2786, doi:10.3762/bjoc.17.188

• methodology based on the trans-stereoselective epoxidation reaction of 2,3-dihydroisoxazoles followed by the regioselective hydrolysis of the corresponding isoxazolidinyl epoxide [15][16]. Very recently, we have reported the synthesis of γ-(hydroxyamino)-α,β-diols by the addition of Grignard reagents to

• isoxazolidine-4,5-diols in the presence of anhydrous cerium chloride [17], which proceeded in a highly syn-diastereoselective manner due to the presence of the unprotected hydroxy group in the α-position. Accordingly, the diol 3 will be examined in the reaction with vinylmagnesium bromide with an emphasis on

• -(hydroxyamino)-α,β-diol 4 (dr > 95:5) in 73% yield (Scheme 3). Its relative configuration was determined by comparison with already reported NMR data of related γ-(hydroxyamino)-α,β-diols [17]. More specifically, the value of the vicinal coupling constant J2,3 = 1.8 Hz and the chemical shift of the H-2 proton

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• corresponding axially chiral biaryl diols 8 were prepared in good yields (60–90%) and excellent enantioselectivities (90–99% ee) in the presence of CPA 2 (Scheme 3). The stereoselectivity of the reaction is only moderately affected by the position and electronic properties of the substituents on the aromatic

Allylic alcohols and amines by carbenoid eliminative cross-coupling using epoxides or aziridines

• Matthew J. Fleming and
• David M. Hodgson

Beilstein J. Org. Chem. 2021, 17, 2385–2389, doi:10.3762/bjoc.17.155

• carbenoids may compete with a desired carbenoid transformation although its value has been demonstrated in, for example, our studies on lithium 2,2,6,6-tetramethylpiperidide (1, LTMP)-induced syntheses of 2-ene-1,4-diols and 2-ene-1,4-diamines from terminal epoxides [3] and aziridines [4][5], respectively

Recent advances in the syntheses of anthracene derivatives

• Giovanni S. Baviera and
• Paulo M. Donate

Beilstein J. Org. Chem. 2021, 17, 2028–2050, doi:10.3762/bjoc.17.131

• ortho-acetal diarylmethanols. Lewis acid-mediated regioselective cyclization of asymmetric diarylmethine dipivalates and diarylmethine diols. BF3·OEt2/CF3SO3H-mediated cyclodehydration reactions of 2-(arylmethyl)benzaldehydes and 2-(arylmethyl)benzoic acids. Synthesis of 2,3,6,7

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

• for the allylation of aldehydes promoted by a dual catalytic system comprising CrCl3 and an iridium-based photocatalyst that was recently developed by Schwarz and co-workers [119]. Similar conditions were further employed to synthesize monoprotected 1,2-homoallylic diols from aldehydes and silyl and

Total synthesis of ent-pavettamine

• Memory Zimuwandeyi,
• Manuel A. Fernandes,
• Amanda L. Rousseau and
• Moira L. Bode

Beilstein J. Org. Chem. 2021, 17, 1440–1446, doi:10.3762/bjoc.17.99

• with careful examination of the preceding steps it became clear that compound 9 was not formed in the reaction of 7 with the sulfoxide auxiliary. Unbeknownst to us at the time, the formation of diol 5 was not as highly selective as expected and this reaction produced two inseparable diols, the desired

Double-headed nucleosides: Synthesis and applications

• Vineet Verma,
• Jyotirmoy Maity,
• Vipin K. Maikhuri,
• Ritika Sharma,
• Himal K. Ganguly and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2021, 17, 1392–1439, doi:10.3762/bjoc.17.98