(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

• in moderate to good yields, employing 2,7-dimethoxythioxanthone (2,2’-OMeTX) as a triplet sensitizer for BCB excitation (Scheme 3A) [38]. Starting from BCB 24, alkenes including styrene derivatives, enol ethers, and vinyl boronates could be incorporated to give 1,2-BCHs (±)-25a–d. Brown and co

Advancements in hydrochlorination of alkenes

• Daniel S. Müller

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

• alkenes remains a commonly employed approach, yielding high yields for styrene derivatives (Scheme 4) [41][42][43]. The example by Theato is remarkable (Scheme 4A), who used HCl (gas) bubbled into neat alkene 13 for 5 hours, and obtained a relatively high yield of the monohydrochlorinated product 14 after

Enhanced reactivity of Li⁺@C₆₀ toward thermal [2 + 2] cycloaddition by encapsulated Li⁺ Lewis acid

• Hiroshi Ueno,
• Yu Yamazaki,
• Hiroshi Okada,
• Fuminori Misaizu,
• Ken Kokubo and
• Hidehiro Sakurai

Beilstein J. Org. Chem. 2024, 20, 653–660, doi:10.3762/bjoc.20.58

• derivatization of this novel material. In this study, we report the synthesis of Li+@C60 derivatives via the thermal [2 + 2] cycloaddition reaction of styrene derivatives, achieving significantly higher yields of monofunctionalized Li+@C60 compared to previously reported reactions. Furthermore, by combining

• range of unsaturated substrates having a relatively lower HOMO level. With the previously uncovered reactivity of Li+@C60 in hand, we synthesized Li+@C60 derivatives in this study through the thermal [2 + 2] cycloaddition of styrene derivatives, which do not react with empty C60 through the same

• of N,N,N',N'-tetraethylethynediamine and 1-morpholino-1-cyclopentene with empty C60 has been reported [17][23], while electron-rich styrene derivatives 1 and 2 can react with empty C60 only through a photoinduced SET pathway [19][22]. From these results, the energy gap between the HOMO of the alkene

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

• 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

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

Cathodic generation of reactive (phenylthio)difluoromethyl species and its reactions: mechanistic aspects and synthetic applications

• Sadanobu Iwase,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2022, 18, 872–880, doi:10.3762/bjoc.18.88

• phenylthiolate anion, which reacts with the starting material 1 to form product 3. In the presence of radical trapping reagents such as styrene derivatives, radical A reacts with styrenes to form radical intermediate adduct C. The radical C abstracts a hydrogen radical to form products 4 and 6. Alternatively

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

• reported a similar approach towards the assembly of 2,2-disubstituted indolines from N-sulfonylanilines and substituted styrene derivatives [93]. In 2014, the Jiao group investigated the carbosulfonation of alkenes 60 for the synthesis of oxindoles 90 through sequential C–S/C–C-bond formation (Scheme 16

• of the aryl ring, a spirocyclic product 145 was formed via a radical cyclization/dearomatization process. Mechanistic investigations revealed the reaction operates through a radical pathway. In 2017, the Li group described a Ag-mediated, Fe-catalyzed alkylarylation of styrene derivatives 115 with α

• examining of other potential arenes capable of undergoing electrophilic aromatic substitution would expand the applicability of the reaction. Carboazidation In 2018, Yang investigated the three-component carboazidation of styrene derivatives 115 with alkanes 101/139b and trimethylsilyl azide for the

Methodologies for the synthesis of quaternary carbon centers via hydroalkylation of unactivated olefins: twenty years of advances

• Thiago S. Silva and
• Fernando Coelho

Beilstein J. Org. Chem. 2021, 17, 1565–1590, doi:10.3762/bjoc.17.112

• ., styrene derivatives [17]) that produce hundreds of tons for polymer synthesis. The goal of this review is to demonstrate the utility of olefins as starting materials in the synthesis of all-carbon quaternary centers through hydroalkylation reactions. Only the hydroalkylation of unactivated olefins as

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

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

• alkenes, electron-rich styrenes, and styrenes with electron-withdrawing substituents in the structure [40]. The yields of the gem-difluorocyclopropanes from the styrene derivatives were almost all excellent. On the other hand, simple alkenes gave lower yields. The reaction of various functionalized

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

• , produced exclusively thietane derivatives 240 and 241 [70] (Scheme 45). The authors further investigated photoreactions of N-substituted monothiophthalimides 237 with styrene derivatives 186 and 242, affording the corresponding spirothietanes 243 and 244 [71] (Scheme 46). They also documented the

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

• -closure (Scheme 12). A wide range of substrates including diverse mono-, di-, and trisubstituted styrene derivatives (21a,i,h, 26a–d and 27a–i) substrates as well as unactivated or deactivated tri- and tetrasubstituted scaffolds (21j,n,o, 26e–g and 27j–o) were efficiently converted. Conclusion The use of

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

• addition (e.g., 351, 352). It was shown that the presence of a heteroatom plays a crucial role due to the otherwise non-selective, facile addition of Cu-Bpin to alkenes (Scheme 56) [103]. Based on previous studies on asymmetric 3-component carboboration of styrene derivatives [104] and 1,3-dienes [105

• electrophiles, such as N-cyanosulfonamides, leading to 1,2 or 4,3-borocyanation in a regiospecific fashion from borocuprative intermediates, respectively [111]. Extending earlier efforts from the Montgomery group for Cu-catalyzed cascade diborylation/ortho-cyanations of terminal allenes [112] and styrene

• derivatives [113], the cyanoborylation of terminal allenes 382 has also been studied. Using B2pin2 in the presence of N-cyano-N-phenyl-p-toluenesulfonamide (NCTs, 377), under Cu-catalysis led to regio-, chemo-, and diastereoselective trifunctionalized products 383–386. The reaction sequence involves three

Recent advances in photocatalyzed reactions using well-defined copper(I) complexes

• Mingbing Zhong,
• Xavier Pannecoucke,
• Philippe Jubault and
• Thomas Poisson

Beilstein J. Org. Chem. 2020, 16, 451–481, doi:10.3762/bjoc.16.42

• irradiation in MeOH to perform the trifluoromethyl methoxylation of styrene derivatives. The methodology was applied to a broad range of styrene derivatives, showing a good functional group tolerance. Noteworthy, α-, β-, and α,β-substituted styrenes were readily functionalized in good to excellent yields. To

• provide a transient radical, which undergoes an intramolecular cyclization to give the aryl radical anion. A final oxidation/deprotonation sequence delivers the product. In 2018, Reiser and co-workers reported the use of the [Cu(dap)2]Cl catalyst in the oxoazidation of styrene derivatives (Scheme 14) [30

• ]. Under green light irradiation, a large panel of styrene derivatives was converted into the corresponding α-azidoketones in good to excellent yields. Interestingly, the reaction was extended to the heteroaromatic derivatives, such as thiophene or benzofuran and to β-substituted styrenes. The authors

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

• the formation of the lactone or the ATRA reaction was obtained by screening a small substrate scope of para-substituted styrene derivatives in the photocatalyzed reaction with monochloroacetic acid using fac-[Ir(ppy)3] as the photocatalyst (Scheme 5). For electron-poor p-halogenated and p

• -trifluoromethylated styrenes no lactone formation took place in these reactions, and only the Kharasch-addition product was observed. The benzylic radical resulting from radical addition to these styrene derivatives seems to be too electron poor for efficient oxidation induced cyclization, thus resulting in a

• of styrene derivatives in the photoredox reaction with monochloroacetic acid. Yields have been determined by 1H NMR spectroscopy of the crude reaction mixture, using 1,3,5-trimethoxybenzene as the external standard. Proposed reaction mechanism. The photoredox formation of 1-(chloromethoxy)-2,2,6,6

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

• Munmun Ghosh,
• Valmik S. Shinde and
• Magnus Rueping

Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264

• potentiostatic electrolysis, styrene derivatives 143 could be transformed into their asymmetric epoxides 144 via direct electrochemical regeneration of FADH2. The authors claimed that this method is superior with respect to substitution of the complex native regeneration cycle, which consists of three enzymes

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• obtained products with stable E-configuration through a SET process. In 2017, Loh and co-workers [141] introduced a Cu(I/II)-catalyzed Cvinyl–H trifluoromethylation of a variety of styrene derivatives. This process was achieved by using 1-methylimidazole (NMI) as ligand and tetrabutylammonium iodide (TBAI

An overview of the cycloaddition chemistry of fulvenes and emerging applications

• Ellen Swan,
• Kirsten Platts and
• Anton Blencowe

Beilstein J. Org. Chem. 2019, 15, 2113–2132, doi:10.3762/bjoc.15.209

• heptafulvenes [18][19][20][21][26][28][227] also participating in such reactions. However, Nair et al. reported that during cycloadditions of 8,8-dicyanoheptafulvene and styrene derivatives (Scheme 16), [8 + 2] and [4 + 2] adducts formed in approximately 1:1 ratio for each styrene variant tested, thus lowering

• and styrene derivatives to afford [8 + 2] and [4 + 2] cycloadducts in a 1:1 ratio [227]. Reaction of 6-aminofulvene and maleic anhydride, showing observed [6 + 2] cycloaddition; the [4 + 2] cycloaddition is not observed [114]. Schemes for Diels–Alder cycloadditions in dynamic combinatorial chemistry

Friedel–Crafts approach to the one-pot synthesis of methoxy-substituted thioxanthylium salts

• Kenta Tanaka,
• Yuta Tanaka,
• Mami Kishimoto,
• Yujiro Hoshino and
• Kiyoshi Honda

Beilstein J. Org. Chem. 2019, 15, 2105–2112, doi:10.3762/bjoc.15.208

• green light irradiation [24][25]. In the course of this study, we found that these thioxanthylium photocatalysts efficiently oxidized styrene derivatives such as trans-anethole, and promoted radical cation Diels–Alder reactions. Based on the background mentioned above, in order to expand the utility of

Synthesis of the aglycon of scorzodihydrostilbenes B and D

• Katja Weimann and
• Manfred Braun

Beilstein J. Org. Chem. 2019, 15, 610–616, doi:10.3762/bjoc.15.56

• particularly attractive as it leads in an atom-economic manner directly to the carbon skeleton of scorzodihydrostilbenes, starting from suitably substituted acetophenone and styrene derivatives. Furthermore, Murai’s protocol offers another advantage: the regioselective formation of the anti-Markovnikov product

Application of olefin metathesis in the synthesis of functionalized polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials

• Patrycja Żak and
• Cezary Pietraszuk

Beilstein J. Org. Chem. 2019, 15, 310–332, doi:10.3762/bjoc.15.28

• , 9-anthracenyl and 2-thienyl have been reported by Marciniec [15]. For all styrene derivatives tested, the procedures described permitted highly regioselective metathesis leading to exclusive formation of the E-isomer. Cross-metathesis experiments were performed under mild reaction conditions (CH2Cl2

Cross metathesis-mediated synthesis of hydroxamic acid derivatives

• Shital Kumar Chattopadhyay,
• Subhankar Ghosh and
• Suman Sil

Beilstein J. Org. Chem. 2018, 14, 3070–3075, doi:10.3762/bjoc.14.285

• 6d–f, respectively. Considerable isomerization (1:1 by 1H NMR) of the CM-product 6d to the corresponding styrene derivative was noticed when HG-II was used in place of G-II. 6e behaved similarly. Reaction with the styrene derivative 4g resulted in low conversion to the CM product 6g (57%). Styrene

• derivatives, belonging to class-I olefins according to Grubbs’ generalizations [31], are indeed known to be a sluggish partner in CM reactions, with homodimerization to stilbene being a recurring problem. Alkenes 4h–j containing a benzyl ester functionality at two, three and four carbons apart, respectively

Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source

• Tetsuaki Fujihara and
• Yasushi Tsuji

Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221

• reductant, carboxyzincation and the four-component coupling reaction between alkyne, acrylates, CO2, and zinc occur efficiently. Rh complexes also catalyze the carboxylation of arylboronic esters, C(sp2)–H carboxylation of aromatic compounds, and hydrocarboxylation of styrene derivatives. The Rh-catalyzed

• hydrocarboxylation of styrene derivatives has been achieved. Furthermore, the formation of pyrones from diynes and CO2 can be effectively catalyzed by Rh complexes. Review Cobalt catalysts Carboxylation of propargyl acetates Allyl and propargyl electrophiles, such as halides and esters, are well known as efficient

• using alkynes [63][64][65][66], alkenes [67][68], allenes [69][70][71] and 1,3-dienes [72][73] have been reported. In this regard, Mikami et al. reported the Rh-catalyzed hydrocarboxylation of styrene derivatives depicted in Scheme 33 [74]. The desired reaction proceeded using [RhCl(cod)]2 as a catalyst

Recent advances in hypervalent iodine(III)-catalyzed functionalization of alkenes

• Xiang Li,
• Pinhong Chen and
• Guosheng Liu

Beilstein J. Org. Chem. 2018, 14, 1813–1825, doi:10.3762/bjoc.14.154

• of styrene derivatives (Scheme 9) [58]. An iodoarene precatalyst 23 bearing the tertiary amide on the lactic side chains was the most effective. mCPBA was used as a stoichiometric oxidant and bismesylimide as an amine source. It is noteworthy that solvent was a key factor to suppress the undesired