Reductive opening of a cyclopropane ring in the Ni(II) coordination environment: a route to functionalized dehydroalanine and cysteine derivatives

• Oleg A. Levitskiy,
• Olga I. Aglamazova,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2022, 18, 1166–1176, doi:10.3762/bjoc.18.121

• radical anions influenced by substituents in the cyclopropane ring are discussed. Optimization of the reaction conditions opens a route to the non-proteinogenic amino acid derivatives containing an α–β or β–γ double C=C bond in the side chain; the regioselectivity can be tuned by the addition of Lewis

• ][26]. Donor–acceptor cyclopropanes constitute an easily available equivalent of all-carbon 1,3-zwitter-ions used in targeted synthesis of various alicyclic as well as carbo- or heterocyclic compounds [27][28][29][30]. The reactive synergy of the three-membered ring and the C–C bond polarization due to

• include disproportionation reaction yielding a mixture of alkenes and the corresponding hydrogenated derivatives, intramolecular cyclization and reaction with external electrophiles. Optimization of the reaction conditions opens a route to amino acid derivatives containing the α-β or β-γ double C=C bond

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

• electrolysis; Introduction Carbon–carbon bond formation is one of the most fundamental and important reactions in synthetic organic chemistry. Reductive coupling of carbonyl compounds known as pinacol coupling would be a powerful method to construct vic-1,2-diol scaffolds through C–C bond formation [1][2

• -2a was subjected to the present reaction conditions, oxidative C–C bond cleavage of dl-2a proceeded to give the corresponding ketone 3a (Scheme 5b) [48]. Recovered 2a was found to be a mixture of dl and meso isomers, indicating that homocoupling of in situ-generated ketone 3a occurred under the

Molecular diversity of the base-promoted reaction of phenacylmalononitriles with dialkyl but-2-ynedioates

• Hui Zheng,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 991–998, doi:10.3762/bjoc.18.99

• base to catalyze the C–C bond formation via a Michael addition of active methylene groups [31]. Therefore, in the presence of TBAB, the bromide assisted with the deprotonation of the phenacylmalononitrile to give a carbanion intermediate A. Secondly, the nucleophilic addition of carbanion A to electron

Morita–Baylis–Hillman reaction of 3-formyl-9H-pyrido[3,4-b]indoles and fluorescence studies of the products

• Nisha Devi and
• Virender Singh

Beilstein J. Org. Chem. 2022, 18, 926–934, doi:10.3762/bjoc.18.92

• medicinal importance is the reason that the synthesis of β-carboline-containing derivatives has been an exciting area for researchers [34][35][36][37][38][39][40]. The Morita–Baylis–Hillman (MBH) reaction is an astonishing C–C bond forming reaction between a carbonyl electrophile and an activated alkene

• . For this purpose, the N-ethyl derivative 9e of 6e was prepared and subjected to MBH reaction with acrylonitrile A and methylacrylate B under neat conditions to generate the corresponding MBH adducts (10eA and 10eB) (Scheme 3). Interestingly, 9e showed more affinity towards this C–C bond forming

Synthetic strategies for the preparation of γ-phostams: 1,2-azaphospholidine 2-oxides and 1,2-azaphospholine 2-oxides

• Jiaxi Xu

Beilstein J. Org. Chem. 2022, 18, 889–915, doi:10.3762/bjoc.18.90

• peroxide and sulfurization with sulfur, respectively (Scheme 16) [37][38]. Synthesis via formation of the C–C bond neighboring at the ring phosphorus atom In 1984, Collins and co-workers attempted the synthesis of benzo-γ-phosphonolactams 56a and 93 from (chloromethyl)(phenyl)-N-methyl-N

• -oxides 56a in 23% and 93 in 63% yields, respectively, showing the limited scope of the synthetic method (Scheme 17) [39]. Ring-closing metathesis (RCM) is an efficient strategy for the construction of cyclic compounds via the formation of a C=C bond [40][41], which can be reduced to the C–C bond. 2

• an efficient method for the synthesis of 1,2-azaphospholidine 2-oxides via the C–C bond formation. Our research group achieved the synthesis of 1-alkyl-3-benzoyl-2-ethoxy-1,3-dihydrobenzo[d][1,2]azaphosphole 2-oxide derivatives 106 from ethyl N-alkyl-N-aryl-1-diazo-2-oxo-2-phenylethylphosphonamidates

Thiophene/selenophene-based S-shaped double helicenes: regioselective synthesis and structures

• Mengjie Wang,
• Lanping Dang,
• Wan Xu,
• Zhiying Ma,
• Liuliu Shao,
• Guangxia Wang,
• Chunli Li and
• Hua Wang

Beilstein J. Org. Chem. 2022, 18, 809–817, doi:10.3762/bjoc.18.81

• )benzene (5c), and S-shaped double helicenes DH-1–3 is shown in Scheme 1. The double oxidative photocyclization of 5a–c is the key step in the synthesis of DH-1–3 because oxidative photocyclization induces double radicals on a double bond, which led to the C=C bond rotation along the resulting single C

Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple

• Alexander S. Filatov,
• Olesya V. Khoroshilova,
• Anna G. Larina,
• Vitali M. Boitsov and
• Alexander V. Stepakov

Beilstein J. Org. Chem. 2022, 18, 769–780, doi:10.3762/bjoc.18.77

• -protonated 1 and C-protonated 1'' tautomers do not contain an enol functional group. It is therefore likely that the lowest stability of the O-protonated form 1' compared to tautomers 1 and 1'' is due to the favorability of the C=O bond over the C=C bond. Next, using the equations recommended by Parr [47

Identification of the new prenyltransferase Ubi-297 from marine bacteria and elucidation of its substrate specificity

• Jamshid Amiri Moghaddam,
• Huijuan Guo,
• Karsten Willing,
• Thomas Wichard and
• Christine Beemelmanns

Beilstein J. Org. Chem. 2022, 18, 722–731, doi:10.3762/bjoc.18.72

• binding abilities to target proteins [3]. The prenylation reaction, most often a C–C-bond-forming step between an aromatic acceptor moiety and a prenyl chain, is catalyzed by dedicated dominantly membrane-bound prenyltransferases (Ptases) [4][5][6][7]. Ptases belonging to the UbiA-superfamily are

• preferences. While the microbial UbiA Ptase catalyzes the C–C-bond formation between an isoprenyl chain and the meta-position of p-hydroxybenzoate (PHB) in the ubiquinone-Coenzyme Q10 biosynthesis (Figure 1), Ptases of type MenA perform the key step in the menaquinone biosynthesis by prenylating 1,4-dihydroxy

Tri(n-butyl)phosphine-promoted domino reaction for the efficient construction of spiro[cyclohexane-1,3'-indolines] and spiro[indoline-3,2'-furan-3',3''-indolines]

• Hui Zheng,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 669–679, doi:10.3762/bjoc.18.68

• aryl group exist on the cis-position of the carbonyl group on the exocyclic C=C bond (Z-configuration). Thus, it can be concluded that the major isomers 3a–z have this kind of the relative configuration. In Figure 3, the aryl group and the carbonyl group of the oxindole scaffold also exist on trans

• -position in the newly formed cyclohexyl ring, while an E-configuration was observed for the exocyclic C=C double bond. Therefore, the major and minor isomers were actually attributable to the Z/E-configuration of the C=C bond, not to the cis/trans-positions in the newly formed cyclohexyl ring. In order to

• of readily available 1,3-dipolarophile, 3-phenacylidenoxindole, was also tested in the reaction. However, it was found that the C=C bond in 3-phenacylidenoxindole was directly reduced to give the corresponding saturated 3-(2-oxo-2-phenylethyl)indolin-2-one. A similar reduction reaction of 3

Unusual highly diastereoselective Rh(II)-catalyzed dimerization of 3-diazo-2-arylidenesuccinimides provides access to a new dibenzazulene scaffold

• Anastasia Vepreva,
• Alexander S. Bunev,
• Andrey Yu. Kudinov,
• Grigory Kantin,
• Mikhail Krasavin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2022, 18, 533–538, doi:10.3762/bjoc.18.55

• intermediate D into cycloheptadiene E is an example of a relatively rare reaction of the cyclopropane-ring expansion through a 1,5-C‒C bond migration [15][16][17]. This concerted process is followed by yet another 1,5-migration of the hydrogen atom, leading to the final dimer 2a. The formation of a single

Sesquiterpenes from the soil-derived fungus Trichoderma citrinoviride PSU-SPSF346

• Wiriya Yaosanit,
• Vatcharin Rukachaisirikul,
• Souwalak Phongpaichit,
• Sita Preedanon and
• Jariya Sakayaroj

Beilstein J. Org. Chem. 2022, 18, 479–485, doi:10.3762/bjoc.18.50

• of C-4 constructed a propenoic acid unit with a 1,1-disubstituted oxymethyl substituent at C-2. The HMBC correlations of H-4 of this unit with C-5, C-6, C-7, and C-10 as well as the chemical shifts of C-4 and C-7 established an ether bond between C-4 and C-7 and a C–C bond between C-4 and C-5 to form

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

Unexpected chiral vicinal tetrasubstituted diamines via borylcopper-mediated homocoupling of isatin imines

• Marco Manenti,
• Leonardo Lo Presti,
• Giorgio Molteni and
• Alessandra Silvani

Beilstein J. Org. Chem. 2022, 18, 303–308, doi:10.3762/bjoc.18.34

• . Interestingly, the molecule does not bear any pseudo-mirror plane, that is, the observed conformer is asymmetric (C1) in itself, regardless the configuration of the two sulfinamide substituents. This peculiarity is likely due to the hindered rotation across the newly formed C–C bond, joining the two oxindole

Regioselectivity of the S_EAr-based cyclizations and S_EAr-terminated annulations of 3,5-unsubstituted, 4-substituted indoles

• Jonali Das and
• Sajal Kumar Das

Beilstein J. Org. Chem. 2022, 18, 293–302, doi:10.3762/bjoc.18.33

• 18 via a concerted protonation and C–C bond formation. Weakened dispersive interactions caused by a substituent or heteroatom resulted in low yields and reduced regioselectivities. In 2020, Li and Van der Eycken and co-workers reported the synthesis of densely functionalized, polycyclic azepino[5,4,3

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

• Surendran Amrutha,
• Sankaran Radhika and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

• emphasis given to green strategies. This is the first review on iron- and cobalt-catalyzed Sonogashira coupling reactions which comprehends literature up to 2020. Keywords: C–C bond formation; cobalt; green reaction; iron; nanoparticles; Sonogashira; Introduction The palladium-catalyzed cross-coupling

• reaction between an aryl/vinyl halide (Cl, Br, I, OTf) and a terminal alkyne in the presence of a Cu(I) co-catalyst under basic conditions to form a Csp2–Csp bond generating an arylalkyne is known as the Sonogashira (Sonogashira–Hagihara) coupling [1] and has become an important C–C bond-forming reaction

Iridium-catalyzed hydroacylation reactions of C1-substituted oxabenzonorbornadienes with salicylaldehyde: an experimental and computational study

• Angel Ho,
• Austin Pounder,
• Krish Valluru,
• Leanne D. Chen and
• William Tam

Beilstein J. Org. Chem. 2022, 18, 251–261, doi:10.3762/bjoc.18.30

• hydride, and C–C bond-forming reductive elimination. Computational results indicate the origin of regioselectivity is involved in the reductive elimination step. Keywords: C–H activation; density functional theory; hydroacylation; iridium catalysis; regioselectivity; Introduction Organic synthesis is

• hydroacylation reactions [74][75][76][77][78], we propose a catalytic cycle utilizing iridium that proceeds with three key steps: (1) iridium(I) oxidative addition into the aldehyde C–H bond, (2) insertion of the olefin into the iridium hydride, and (3) C–C bond-forming reductive elimination. The hydroacylation

• last key step in the catalytic cycle involves the C–C bond-forming reductive elimination to form the final ketone intermediate IN3a or IN3b (Figure 1). Two possible transition states, 2aTS3a and 2bTS3b, can be located. The concerning free energy barrier about IN2a to IN3a, via 2aTS3a is 10.8 kcal/mol

1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

• Ruan Carlos B. Ribeiro,
• Patricia G. Ferreira,
• Amanda de A. Borges,
• Luana da S. M. Forezi,
• Fernando de Carvalho da Silva and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 53–69, doi:10.3762/bjoc.18.5

• exhibiting solid-state fluorescence, although the fluorescence partially disappears in solution, and there is a large shift to red and blue [98][99]. Carbon–carbon bond formation The main steps in a synthesis usually involve C–C bond formation, which is usually the main reaction step, or functional group

• transformations. Organometallics are the most commonly used catalysts to promote C–C bond formation. In addition, other so-called classical reactions are also widely used, such as Friedel–Crafts alkylation and acylation, Wittig and Horner–Emmons reactions, carbonyl addition/substitution, α-alkylation, aldol

• )phenyl]ethylene in acetic acid efficiently produced 4-vinyl-1,2-naphthoquinones 55 and 4-aryl-1,2-naphthoquinones 56a,b, respectively, under nickel(II) catalysis, forming a C–C bond (Scheme 16) [103]. When the reaction was carried out in 10% aqueous methanol solution at room temperature for 5 hours, 56b

A photochemical C=C cleavage process: toward access to backbone N-formyl peptides

• Haopei Wang and
• Zachary T. Ball

Beilstein J. Org. Chem. 2021, 17, 2932–2938, doi:10.3762/bjoc.17.202

• contrast, photorelease systems based on C–C or C=C bond photocleavage are quite rare [14][15]. We recently reported a vinylogous analogue of this photo-deprotection process, which allowed photocleavage of alkenyl sp2 C–X bonds, rather than benzylic sp3 C–X cleavage [16][17]. We now report that further

• , which leads to formyl products from formal oxidative cleavage of a C=C bond. Our interest in vinylogous analogues of 2-nitroaryl photoreactive groups stems from studies into alkenylboronic acid reagents for Chan–Lam-type modification of peptide backbone N–H bonds, directed by a proximal histidine

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• significant development over the past 10 years. First achieved by Li and co-workers in 2007 [44], cross-dehydrogenative-coupling (CDC) reactions offer a highly atom economic approach to carbon–carbon (C–C) and carbon–heteroatom (C–X) bond formation via C–H activation [45][46]. Generally speaking, C–C bond

• forming reactions can be classified into three types (Scheme 1): the reaction of a compound bearing functional group (X), coupling with another compound bearing functional group (Y), producing a new C–C bond through the formation of X–Y (Scheme 1a). Secondly, the reaction of a C–H compound with a C–X

• functionalized compound (Scheme 1b). Lastly, the reaction between two C–H compounds to form a C–C bond, formally eliminating H2, hence the dehydrogenative reference (Scheme 1c). As this coupling reaction does not require functionalization prior to coupling, it shortens the synthetic route, and lowers the

The PIFA-initiated oxidative cyclization of 2-(3-butenyl)quinazolin-4(3H)-ones – an efficient approach to 1-(hydroxymethyl)-2,3-dihydropyrrolo[1,2-a]quinazolin-5(1H)-ones

• Alla I. Vaskevych,
• Nataliia O. Savinchuk,
• Ruslan I. Vaskevych,
• Eduard B. Rusanov,
• Oleksandr O. Grygorenko and
• Mykhailo V. Vovk

Beilstein J. Org. Chem. 2021, 17, 2787–2794, doi:10.3762/bjoc.17.189

• 13. The formation of the last-mentioned can be achieved by an initial PIFA attack on the homoallyl C=C bond [41][42][57][58] through the possible intermediates 14 and 15 alternatively (pathway b). Finally, alkaline hydrolysis of 13 upon work-up of the reaction mixture leads to the formation of target

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

• I-15 leads to enamine I-16. In the presence of the CPA catalyst, an intramolecular Michael addition of the amino group to the enamine in I-16 leads to I-17. Subsequently, the imines I-15 and I-17 are converted to the intermediate I-18, which through elimination by cleavage of the C–C bond gives the

Synthesis of highly substituted fluorenones via metal-free TBHP-promoted oxidative cyclization of 2-(aminomethyl)biphenyls. Application to the total synthesis of nobilone

• Ilya A. P. Jourjine,
• Lukas Zeisel,
• Jürgen Krauß and
• Franz Bracher

Beilstein J. Org. Chem. 2021, 17, 2668–2679, doi:10.3762/bjoc.17.181

• aldehyde (33%) being generated (Table 2, entry 11). Similar results were obtained when adding iodine to promote benzylic oxidation [56] (Table 2, entry 12). Finally, Pd(OAc)2 was added in hopes of improving the mediation of C–C bond formation [38] (Table 2, entry 13). Interestingly, here the yield of

Ligand-dependent stereoselective Suzuki–Miyaura cross-coupling reactions of β-enamido triflates

• Tomáš Chvojka,
• Athanasios Markos,
• Svatava Voltrová,
• Radek Pohl and
• Petr Beier

Beilstein J. Org. Chem. 2021, 17, 2657–2662, doi:10.3762/bjoc.17.179

• causes the tautomerization of complex 5 [30] to zwitterionic carbene 6 which can now isomerize through the C–C bond rotation to the thermodynamically more stable palladium complex 7, followed by reductive elimination to enamide 3. A possible isomerization of enamides 2 or 3 in the presence of a catalyst

Silica gel and microwave-promoted synthesis of dihydropyrrolizines and tetrahydroindolizines from enaminones

• Robin Klintworth,
• Garreth L. Morgans,
• Stefania M. Scalzullo,
• Charles B. de Koning,
• Willem A. L. van Otterlo and
• Joseph P. Michael

Beilstein J. Org. Chem. 2021, 17, 2543–2552, doi:10.3762/bjoc.17.170

• prior to acid-promoted cyclization cannot be ruled out, since conjugation in the push–pull system should weaken the C=C bond and lower its rotational barrier [20]. Similar enaminone isomerizations have been detected even at room temperature [48]. If thermal isomerization indeed takes place, then one

• , was reported as recently as 2018 [55]. More interestingly, conventional heating in acetic acid of an enaminone bearing a phenacylsulfanyl substituent adjacent to nitrogen on the C=C bond produced ethyl pyrrolo[2,1-b]thiazole-5-carboxylates in moderate yield, while the corresponding microwave-assisted

Visible-light-mediated copper photocatalysis for organic syntheses

• Yajing Zhang,
• Qian Wang,
• Zongsheng Yan,
• Donglai Ma and
• Yuguang Zheng

Beilstein J. Org. Chem. 2021, 17, 2520–2542, doi:10.3762/bjoc.17.169

• oxime esters 73 formed cyclic iminyl radicals, which then formed cyanoalkyl radicals through a selective β-C–C bond scission. This protocol was further applied to the aminocarbonylation of cycloketone oxime esters with CO gas and amines 74. Cycloketone oxime esters are reduced by the photoexcited [LnCuI

• –NHR]* complex C or the ground-state LnCuI–NHR species B to generate a cyclic iminyl radical 73a-A, which oxidizes the LnCuII–NHR complex D (Scheme 30, path a or b). Subsequently, radical 73a-A undergoes a β-C–C bond scission to provide the cyanoalkyl radical 73a-B, which is trapped by complex D and