Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

• Radell Echemendía,
• Carlee A. Montgomery,
• Fabio Cuzzucoli,
• Antonio C. B. Burtoloso and
• Graham K. Murphy

Beilstein J. Org. Chem. 2024, 20, 3182–3190, doi:10.3762/bjoc.20.263

• reported the α-alkylation of carbonyl sulfoxonium ylides via a Michael addition approach that occurred without any competition from cyclopropanation [30]. While this reaction represented the first direct alkylation of sulfoxonium ylides, it was nonetheless limited to the more reactive ester ylide variants

1,2-Difluoroethylene (HFO-1132): synthesis and chemistry

• Liubov V. Sokolenko,
• Taras M. Sokolenko and
• Yurii L. Yagupolskii

Beilstein J. Org. Chem. 2024, 20, 1955–1966, doi:10.3762/bjoc.20.171

• -difluoroethylene. Cyclopropanation of 1,2-difluoroethylene. Diels–Alder reaction of 1,2-difluoroethylene and hexachlorocyclopentadiene. Cycloaddition reaction of 1,2-difluoroethylene and fluorinated ketones. Cycloaddition reaction of 1,2-difluoroethylene and perfluorinated aldehydes. Photochemical cycloaddition of

(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

• cyclopropanation [44] (to (±)-66) of α-hydroxy silyl enol ethers (±)-65 followed by an acid-catalysed pinacol rearrangement to (±)-67. As exemplary derivatizations of 5-oxo-BCH (±)-67, 1,5-BCHs (±)-68, (±)-69 and (±)-70 were accessed by reductive amination, ketone reduction, and Horner–Wadsworth–Emmons olefination

• of bridge difluorinated BCPs from α-allyldiazoacetates. In their reaction sequence, intramolecular cyclopropanation first forms the bicyclobutane which is then subjected to CF2 carbene insertion to yield the BCP [76]. Another useful pathway to 1,2,3-BCPs is strain release functionalisation as was

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

• -stage C–H functionalization of arenes, Wickens’s group has introduced an oxidative alkene aziridination strategy that relies on thianthrenation of an alkene under electrochemical conditions [27]. Subsequently, cyclopropanation, [28] aziridination, [29] allylic C–H functionalization, [30][31] transition

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• have been feasible. In 1989, Moriarty was investigating the intramolecular cyclopropanation of 10 under copper-catalysis, presuming that the reaction would proceed through a metallocarbene intermediate [113]. However, a control experiment showed the reaction to also be viable without catalyst, from

• which the expected product of a free carbene-derived Wolff-type rearrangement was not observed (Scheme 2b). Likewise, Gallos et al. were investigating the intramolecular cyclopropanation of ylide 12, and found that the metal-free reaction proceeded with identical yield and diastereoselectivity as did

• iodobenzene gave 19, and extrusion of SO2 gave 20. In 2010, Moriarty revisited their earlier transformation and reported that the metal-free intramolecular cyclopropanation of 10 to 11 could be achieved in an improved 95% yield by performing the reaction at room temperature rather than 0 °C [11]. The reaction

Copper-catalyzed N-arylation of amines with aryliodonium ylides in water

• Kasturi U. Nabar,
• Bhalchandra M. Bhanage and
• Sudam G. Dawande

Beilstein J. Org. Chem. 2023, 19, 1008–1014, doi:10.3762/bjoc.19.76

• , catalyzed by a copper catalyst [39]. Murphy and co-workers reported blue LED-mediated metal-free cyclopropanation of alkenes with iodonium ylides through a diradical intermediate [40]. However, iodonium ylides are relatively unexplored for the arylation of amines. So far only Spyroudis’s group reported N

First synthesis of acylated nitrocyclopropanes

• Kento Iwai,
• Rikiya Kamidate,
• Khimiya Wada,
• Haruyasu Asahara and
• Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2023, 19, 892–900, doi:10.3762/bjoc.19.67

• ), was subjected to cyclopropanation according to a method described in the literature [13]. To a solution of adduct 4b in toluene, (diacetoxyiodo)benzene and tetrabutylammonium iodide were added, and the resulting mixture was stirred at room temperature for 14 h. Unexpectedly, from the reaction mixture

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

Access to cyclopropanes with geminal trifluoromethyl and difluoromethylphosphonate groups

• Ita Hajdin,
• Romana Pajkert,
• Mira Keßler,
• Jianlin Han,
• Haibo Mei and
• Gerd-Volker Röschenthaler

Beilstein J. Org. Chem. 2023, 19, 541–549, doi:10.3762/bjoc.19.39

• -pentafluoropropylphosphonate, bearing a trifluoromethyl and a difluoromethyl group is reported for the first time. Its application in CuI-catalyzed cyclopropanation reactions with aromatic and aliphatic terminal alkenes under mild reaction conditions is demonstrated. In total, sixteen new cyclopropanes were synthesized in

• good to very good yields. Keywords: alkenes; cyclopropanation; diazo compounds; difluoromethylphosphonate; DFT calculations; Introduction Cyclopropanes constitute a fascinating class of organic compounds due to their unique structure and bond properties [1]. However, their synthetic utility is

• ]. Therefore, as relevant building blocks, tremendous efforts have been made to develop reliable methods for their synthesis. Transition-metal-catalyzed cyclopropanation of alkenes with trifluoromethyldiazoalkanes is a commonly used synthetic strategy for the construction of trifluoromethylcyclopropanes

1,4-Dithianes: attractive C2-building blocks for the synthesis of complex molecular architectures

• Bram Ryckaert,
• Ellen Demeyere,
• Frederick Degroote,
• Hilde Janssens and
• Johan M. Winne

Beilstein J. Org. Chem. 2023, 19, 115–132, doi:10.3762/bjoc.19.12

• expected allyl cation (3 + 2) cycloaddition reactivity is not operating under gold(I) catalysis, but instead it behaved as a reliable and quite stereoselective vinylgold carbenoid species, affording exclusively cyclopropanation products with a wide range of olefin substrates (Scheme 18c). The carbene-type

• formation of the cis-vinylcyclopropanes (Scheme 18c and 18d). Desulfurization of the adducts again yields the product of a formal cyclopropanation with a ‘naked’ vinyl carbene species, as demonstrated by the stereoselective synthesis of the protected cis-2-vinylcyclopropan-1-amine 123 (Scheme 18d). 7

Total synthesis of grayanane natural products

• Nicolas Fay,
• Rémi Blieck,
• Cyrille Kouklovsky and
• Aurélien de la Torre

Beilstein J. Org. Chem. 2022, 18, 1707–1719, doi:10.3762/bjoc.18.181

• synthesis started from 3-hydroxy-2-methoxybenzaldehyde (34), which was converted into Grignard reagent 35 and added onto 3-methylbut-2-enal (Scheme 6). A sequence involving Claisen rearrangement, Roskamp homologation, diazo transfer and intramolecular cyclopropanation led to intermediate 37. The hydroxy

• and 23 steps) to access grayananes with a cyclopentenone moiety on the A ring. It should be noted that although this is a racemic synthesis, intermediate 37 was also synthesized in enantioenriched form using a chiral copper catalyst for the cyclopropanation and a chiral auxiliary on the ester moiety

Synthetic study toward the diterpenoid aberrarone

• Liang Shi,
• Zhiyu Gao,
• Yiqing Li,
• Yuanhao Dai,
• Yu Liu,
• Lili Shi and
• Hong-Dong Hao

Beilstein J. Org. Chem. 2022, 18, 1625–1628, doi:10.3762/bjoc.18.173

• were reported [30][31] and more recently, Carreira and co-workers reported [32] the first total synthesis of aberrarone through an impressive cascade reaction including a gold-catalyzed Nazarov cyclization, a cyclopropanation followed by intramolecular aldol reaction to forge the A, B and D rings

Electrogenerated base-promoted cyclopropanation using alkyl 2-chloroacetates

• Kouichi Matsumoto,
• Yuta Hayashi,
• Kengo Hamasaki,
• Mizuki Matsuse,
• Hiyono Suzuki,
• Keiji Nishiwaki and
• Norihito Kawashita

Beilstein J. Org. Chem. 2022, 18, 1116–1122, doi:10.3762/bjoc.18.114

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

• formation of a single diastereomer at the cyclopropanation step can be explained by the preferred approach of carbene A from the least sterically hindered side of indene C and the π-stacking interaction of the aromatic fragment of indene and the benzylidene substituent of the carbene. The conversion of

Strategies for the synthesis of brevipolides

• Yudhi D. Kurniawan and
• A'liyatur Rosyidah

Beilstein J. Org. Chem. 2021, 17, 2399–2416, doi:10.3762/bjoc.17.157

• –Smith cyclopropanation; Hyptis brevipes Poit; ring-closing metathesis; Introduction Hyptis brevipes Poit. is an invasive plant species belonging to the mint family Lamiaceae [1][2][3][4]. This plant has been reported to originate from tropical America but is now distributed broadly in other tropical

• commercially available (E)-p-methoxycinnamic acid (17). The vital intermediate 16 is expected from cyclopropyl epoxy alcohol 18, which in turn can be prepared from allylic alcohol 19 via the Furukawa-modified Simmons–Smith cyclopropanation and VO-mediated epoxidation. Acetylfuran (20) is chosen as the six

• influence the stereo-outcome for the later cyclopropanation step. Thus, treatment of 25 with diethylzinc and diiodomethane delivered the expected syn-cyclopropyl carbinol 26 as the major diastereomer (dr 95:5) in 90% yield. After the protection of the secondary alcohol as MOM ether, the primary alcohol was

Asymmetric organocatalyzed synthesis of coumarin derivatives

• Natália M. Moreira,
• Lorena S. R. Martelli and
• Arlene G. Corrêa

Beilstein J. Org. Chem. 2021, 17, 1952–1980, doi:10.3762/bjoc.17.128

• of spiroonxindole-cyclopropa[c]coumarins 75 through the cyclopropanation of 3-acylcoumarins 43 and 3-halooxindoles 74 [58]. The authors chose a quinine-derived squaramide catalyst 73 to perform the [2 + 1] cycloaddition. This catalyst reacts with 3-halooxindole, generating an ammonium salt which is

Synthesis of β-triazolylenones via metal-free desulfonylative alkylation of N-tosyl-1,2,3-triazoles

• Soumyaranjan Pati,
• Renata G. Almeida,
• Eufrânio N. da Silva Júnior and
• Irishi N. N. Namboothiri

Beilstein J. Org. Chem. 2021, 17, 762–770, doi:10.3762/bjoc.17.66

• many bioactive heterocycles [36]. These are also important precursors of diazo adducts which are used in insertion, cyclopropanation, and various rearrangements to construct various cyclic as well as acyclic moieties under metal-catalysed conditions [37][38]. On the contrary, under basic conditions

[2 + 1] Cycloaddition reactions of fullerene C₆₀ based on diazo compounds

• Yuliya N. Biglova

Beilstein J. Org. Chem. 2021, 17, 630–670, doi:10.3762/bjoc.17.55

• promising. They are synthesized in two main reactions: nucleophilic cyclopropanation according to the Bingel method and thermal addition of diazo compounds. This present review summarizes the material on the synthesis of monofunctionalized methanofullerenes – analogues of [60]PCBM – based on various diazo

• ]PCBM; diazo compounds; mechanisms and optimal conditions of cyclopropanation; methanofullerenes C60; Introduction Taking into consideration that all life on Earth is of organic origin. with carbon as its basic element (20% by weight of every living organism, and the fourth most abundant element in the

• processes, among which reactions leading to methanofullerenes are widely used. Two main synthetic methods for the production of methanofullerenes can be distinguished (Scheme 1): nucleophilic cyclopropanation with stabilized carbanions that occurs by the addition–cleavage mechanism – the Bingel reaction (I

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

• activity; cyclopropanation; difluorocyclopropane derivatives; synthesis; Introduction The chemistry of cyclopropane derivatives is one of the most intensively developing fields of organic chemistry. In the past decade there have been made many investigations to develop new chemo-, regio- and

• difluorocyclopropane and its derivatives can be distinguished: carbene and non-carbene methods of cyclopropanation along with functional group transformations of existing cyclopropanes. The most popular route to prepare fluorocyclopropanes is to generate fluorine-containing carbenes (or carbenoids), which then react

• with multiple bonds, resulting in cyclopropanation. One of the important properties of fluorine-containing carbenes and carbenoids is their electrophilicity, which is a result of the high electronegativity of fluorine. Also, fluorine has an +M effect which tends to reduce the reactivity of the carbenes

Au(III) complexes with tetradentate-cyclam-based ligands

• Ann Christin Reiersølmoen,
• Thomas N. Solvi and
• Anne Fiksdahl

Beilstein J. Org. Chem. 2021, 17, 186–192, doi:10.3762/bjoc.17.18

• ; cyclam derivatives; cyclopropanation; Introduction The importance of gold for humankind dates long back, and gold is linked to the evolution of many parts of the society. Contrary to the general fascination and importance of gold, the potential as homogenous catalyst has been neglected, compared to a

• cyclopropanation of styrene with propargyl ester [49][50][51][52] (Table 1) were selected as test reactions. These reactions have previously been studied with different gold(I) and gold(III) catalysts and a variety of substrates, thus providing a solid background for comparison. A large difference in the catalytic

• ) catalysis of the cyclopropanation reaction, where complex 5a-Au(III) and 6a-Au(III) gave full conversion in 1 hour and 12 hours, respectively (Table 1, entries 4 and 5). The cyclopropyl product 11 was obtained in >90% yield and high cis diastereoselectivity (up to 74% de), similar to our previous studies

Synthesis of novel fluorinated building blocks via halofluorination and related reactions

• Attila Márió Remete,
• Tamás T. Novák,
• Melinda Nonn,
• Matti Haukka,
• Ferenc Fülöp and
• Loránd Kiss

Beilstein J. Org. Chem. 2020, 16, 2562–2575, doi:10.3762/bjoc.16.208

• interactions are marked with blue two-headed arrows. Mechanism of the reaction of the cyclopropanation of the compounds (rac)-2a,b and (rac)-5a with t-BuOK. Presumed mechanism of the reaction of the compound (rac)-6b with t-BuOK. Cyclizations of halofluorinated tetrahydrophthalimides with DBU. Relevant NOESY

Copper catalysis with redox-active ligands

• Agnideep Das,
• Yufeng Ren,
• Cheriehan Hessin and
• Marine Desage-El Murr

Beilstein J. Org. Chem. 2020, 16, 858–870, doi:10.3762/bjoc.16.77

• cyclopropanation through a strained redox-active ligand framework reminiscent of the entatic state model. Products are obtained as a mixture of cis and trans isomers. Funding This work has been supported through funding from the Université de Strasbourg, CNRS, IDEX Excellence Initiative (AD), Emergence Sorbonne

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

• alcohol due to decomposition. Nonetheless, several products could be transformed into molecules of greater complexity. For example, cyclopropanation could be achieved to give 269. Additionally, TBS protection of 268 followed by ring closing metathesis (RCM) led to the interesting 6-membered silacycle 270

Synthesis of organic liquid crystals containing selectively fluorinated cyclopropanes

• Zeguo Fang,
• Nawaf Al-Maharik,
• Peer Kirsch,
• Matthias Bremer,
• Alexandra M. Z. Slawin and
• David O’Hagan

Beilstein J. Org. Chem. 2020, 16, 674–680, doi:10.3762/bjoc.16.65

• 18 in a very straightforward manner, and the product could be isolated by chromatography in 72% yield [17]. This olefin was then subject to a difluorocarbene cyclopropanation using TMSCF3 and NaI, and this generated both isomers, 11a and 11b, in a ratio of 5:1, respectively. After three

Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid

• Kaj M. van Vliet,
• Nicole S. van Leeuwen,
• Albert M. Brouwer and
• Bas de Bruin

Beilstein J. Org. Chem. 2020, 16, 398–408, doi:10.3762/bjoc.16.38

• decarboxylative activation we anticipated its possibilities in cyclopropanation. The chloromethyl radical generation by photoredox catalysis is a useful strategy for cyclopropanation [58]. Most photoredox catalyzed, decarboxylative generations of carbon-centered radicals are based on the formation of “stabilized

• cyclopropanation. We have screened a series of strongly oxidizing photoredox catalysts and various alkenes, but unfortunately we were thus far unsuccessful in obtaining cyclopropane derivatives (see experimental section). Conclusion We have shown that it is possible to use monochloroacetic acid to form two types

• chloromethyl radical can be formed with photoredox catalysis from monochloroacetic acid, but we were not yet able to apply such reactions in a productive manner, such as in cyclopropanation reactions. A part of the industry around monochloroacetic acid. Cyclic voltammogram of monochloroacetic acid and