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

• and S–S bonds. A plausible mechanism for the metal-catalyzed acylation and acylthiolation is illustrated in Scheme 33. Firstly, oxidative addition of palladium to the C–S bond of NTSE 1’’’ afforded intermediate I. The transmetalation from boron to palladium led to intermediate III, followed by

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

• may be mentioned here that the complexes [(SIPr)CuX] (X = Cl, Br, I) were also prepared through transmetalation, a method that will be discussed later. In contrast to the aforementioned complexes, [(IMes)CuX] and [(SIMes)CuX] (X = Cl, Br) were best prepared from the corresponding NHC·HCl precursors

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• corresponding C2-arylated products 127 in good to excellent yields with high site selectivity. A catalytic mechanism was proposed in which the electrophilic C–H palladation of pyridine N-oxide 9 occurs preferentially at the C-2 position leading to heterocoupling intermediate 128. Subsequent transmetalation

• followed by transmetalation with CuI pyridyl species 133 generated from the reaction of Cu2O with the methylated pyridine to afford intermediate 134 that on reductive elimination results in salt 135. Subsequent demethylation of 135 gives monoarylated product 136 or the intermediate 135 reenters the

• (Scheme 30). The reaction showed good compatibility with various functional groups. The proposed mechanism (Scheme 30b) involves the silver-catalyzed decarboxylation of heteroaryl acid 156 followed by transmetalation providing palladium intermediate 160. Further, C–H activation of pyridine N-oxide 9

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

• their control experiments and literature mechanistic studies (Chegondi et al.) [84], the role of the base (LiOt-Bu) was considered. Following the Cu-catalyzed conjugate addition of B2pin2, the Michael cyclization is facilitated by the transmetalation of stoichiometric Li base with the Cu enolate (Scheme

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• 25. Transmetalation of 25 with the organoboronic acid gives intermediate 26, which upon reductive elimination affords the difunctionalized product 21 and regenerates the Ni(0) catalyst. In 2019, the Stanley laboratory explored the Ni-catalyzed intermolecular three-component carboacylation of

• to afford the acyl–Ni(II)–amido intermediate 30. Side-on coordination followed by migratory insertion of the bicyclic alkene selectively generates the exo-alkyl–Ni(II)–amido complex 31. Transmetalation with triarylborane affords 32 which undergoes reductive elimination to form the carboacylated

• –Cu species 60 which after electrophilic amination with the O-benzoylhydroxylamine 54 liberates the final aminoborylated product 55 and a benzoyl–Cu complex 61. To close the catalytic cycle a transmetalation of 61 with LiOt-Bu regenerates the active catalyst. In 2017, Xiao and Fu studied the Cu

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

• °C and 0 °C, temperatures at which these organometallic reagents are also reported to be quite stable. The zincated dithiins can also be prepared by transmetalation of the magnesiated dithiins at −30 °C, and these organozinc reagents can then be used in room temperature Pd-catalyzed cross-coupling

Rhodium-catalyzed intramolecular reductive aldol-type cyclization: Application for the synthesis of a chiral necic acid lactone

• Motoyuki Isoda,
• Kazuyuki Sato,
• Kenta Kameda,
• Kana Wakabayashi,
• Ryota Sato,
• Hideki Minami,
• Yukiko Karuo,
• Atsushi Tarui,
• Kentaro Kawai and
• Masaaki Omote

Beilstein J. Org. Chem. 2022, 18, 1642–1648, doi:10.3762/bjoc.18.176

• complex 5 from [RhCl(cod)]2 and Et2Zn would generate predominantly the corresponding E-enolate 6 via 1,4-reduction, which is stabilized through η6 binding with benzene ring of the substrate. Subsequent transmetalation with zinc species 4 readily reacts with the carbonyl group to form the intramolecular C

Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 2450–2461, doi:10.3762/bjoc.17.162

• transmetalation. The use of dioxane instead of toluene (Table 1, entry 11) gave again a very good yield (89%). However, the employment of THF resulted in a decreased yield (Table 1, entry 10). The best result for the Suzuki–Miyaura cross-coupling between 2 and 3a was obtained using 1 mol % of Pd(PPh3)4 and 4

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

• –H activation involving carbon–metal bond or a mechanism involving the usual metal-mediated coupling pathways comprising oxidative addition, transmetalation and reductive elimination steps, they are beyond the scope of this review and will not be extensively covered herein. Homogeneous and

Recent advances in palladium-catalysed asymmetric 1,4–additions of arylboronic acids to conjugated enones and chromones

• Jan Bartáček,
• Jan Svoboda,
• Martin Kocúrik,
• Jaroslav Pochobradský,
• Alexander Čegan,
• Miloš Sedlák and
• Jiří Váňa

Beilstein J. Org. Chem. 2021, 17, 1048–1085, doi:10.3762/bjoc.17.84

• -up report of the Miyaura group in 2007 provided an experimental protocol that allowed the addition of arylboronic acids instead of aryltrifluoroborates [34]. The previously used catalysts PdL1a,b were combined with additional silver salts (AgBF4 or AgSbF6) that greatly accelerated the transmetalation

• arylboronic acids reacted much slower or did not react at all due to the slow transmetalation to Pd (entries 7 and 8, Table 7) [37]. The addition of phenylboronic acid (or aprotic triphenylboroxine with slow addition of water to the reaction mixture) was also tested in combination with enones differing in

Using multiple self-sorting for switching functions in discrete multicomponent systems

• Amit Ghosh and
• Michael Schmittel

Beilstein J. Org. Chem. 2020, 16, 2831–2853, doi:10.3762/bjoc.16.233

• backbones in the presence of Ag2O provided exclusively the three homomeric cylinders [Ag3(13)2]3+, [Ag3(14)2]3+, and [Ag3(15)2]3+ (state: SelfSORT-I in Figure 7). Upon the addition of gold(I) ions, a one-pot transmetalation triggered an exchange of the Ag+ ions for Au+ in the tris-NHC ligand-based cylinders

• (SelfSORT-II). Such type of transmetalation in metal–NHC complexes with a retention of the individual homomeric supramolecular assemblies has not been reported in literature. Recently, a quantitative and reversible structural interconversion of supramolecular structures was achieved by the inclusion and

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

Regioselective cobalt(II)-catalyzed [2 + 3] cycloaddition reaction of fluoroalkylated alkynes with 2-formylphenylboronic acids: easy access to 2-fluoroalkylated indenols

• Tatsuya Kumon,
• Miroku Shimada,
• Jianyan Wu,
• Shigeyuki Yamada and
• Tsutomu Konno

Beilstein J. Org. Chem. 2020, 16, 2193–2200, doi:10.3762/bjoc.16.184

• -fluoroalkylated indanones are shown in Scheme 5 [28][38]. Thus, the reaction presumably proceeds as follows: (1) transmetalation of the cobalt catalyst with 2-formylphenylboronic acids (2) gives the arylcobalt species Int-1, (2) insertion of the alkyne 1 into the [Co]–Ar bond (see Int-2a) [39], (3) migration

Syntheses of spliceostatins and thailanstatins: a review

• William A. Donaldson

Beilstein J. Org. Chem. 2020, 16, 1991–2006, doi:10.3762/bjoc.16.166

• , followed by a transmetalation provided a vinylzinc reagent that was coupled with 48 to afford 128, for which only the E-stereoisomer was observed. Notably, the Negishi conditions were tolerant to the azide present in 48 and the oxirane and 1° iodoalkane present in 91. The subsequent reduction of the azide

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147

Palladium-catalyzed regio- and stereoselective synthesis of aryl and 3-indolyl-substituted 4-methylene-3,4-dihydroisoquinolin-1(2H)-ones

• Valeria Nori,
• Antonio Arcadi,
• Armando Carlone,
• Fabio Marinelli and
• Marco Chiarini

Beilstein J. Org. Chem. 2020, 16, 1084–1091, doi:10.3762/bjoc.16.95

• halides [38], α-iodoenones [39], or by transmetalation of a Pd(II) species with boronic acids [33]. In this context, we decided to explore the use of substrates 2 in the reaction with 2-alkynyltrifluoroacetanilides 5 through a sequential cyclocarbopalladation/aminopalladation/reductive elimination process

• containing electron-donating substituents; electron-poor arylboronic acids proved to be slightly less effective, probably because of their lower nucleophilicity that could have affected the transmetalation step. Moreover, we screened the reaction of a number of aromatic boronic acids 3a–j with a set of N

Copper-catalyzed enantioselective conjugate reduction of α,β-unsaturated esters with chiral phenol–carbene ligands

• Shohei Mimura,
• Sho Mizushima,
• Yohei Shimizu and
• Masaya Sawamura

Beilstein J. Org. Chem. 2020, 16, 537–543, doi:10.3762/bjoc.16.50

• protons of the acidic imidazolium C–H and phenol O–H groups of the L4·HBF4 adduct in the presence of CuCl to generate a phenoxy copper(I) species A. As a result, all LiOt-Bu (20 mol %) is consumed in this step. Thus, the system is neutral. Transmetalation between A and (EtO)2MeSiH produces the copper

• hydride species B. This transmetalation adds the silyl group to the phenoxy oxygen atom of the NHC ligand. The coordination of an α,β-unsaturated carbonyl compound 1 to the copper atom occurs in such a way that the bulky O-silyl group of the copper catalyst can avoid steric repulsions with the

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• accessible using the transmetalation route B and C from compound 100 and 101, respectively. The phenyl phosphine derivatives, using the metal-catalyzed phosphorylation route A, and lower yields (14%) were obtained compared to the transmetalation route C. P–H Bond addition to unsaturated precursors The

A new approach to silicon rhodamines by Suzuki–Miyaura coupling – scope and limitations

• Thines Kanagasundaram,
• Antje Timmermann,
• Carsten S. Kramer and
• Klaus Kopka

Beilstein J. Org. Chem. 2019, 15, 2569–2576, doi:10.3762/bjoc.15.250

• ). Again, the reaction catalyzed by PdCl2(dppf) resulted in an enhanced yield compared to catalysis with PdCl2(PPh3)2. Next we aimed at the synthesis of a silicon rhodamine bearing an acid function in 2’-position. With a less bulky methyl ester in the 2’-position of the phenylboroxine, the transmetalation

Functionalization of 4-bromobenzo[c][2,7]naphthyridine via regioselective direct ring metalation. A novel approach to analogues of pyridoacridine alkaloids

• Benedikt C. Melzer,
• Alois Plodek and
• Franz Bracher

Beilstein J. Org. Chem. 2019, 15, 2304–2310, doi:10.3762/bjoc.15.222

• ]. Reaction of allyl iodide (17) with metalated 9d after addition of catalytic amounts of CuCN∙2LiCl led to the formation of the 5-allyl compound 18 in 37% yield. Metalation of 9d using TMPMgCl∙LiCl and subsequent transmetalation with ZnCl2 followed by Negishi cross-coupling reaction in the presence of Pd(dba

Borylation and rearrangement of alkynyloxiranes: a stereospecific route to substituted α-enynes

• Ruben Pomar Fuentespina,
• José Angel Garcia de la Cruz,
• Gabriel Durin,
• Victor Mamane,
• Jean-Marc Weibel and
• Patrick Pale

Beilstein J. Org. Chem. 2019, 15, 1416–1424, doi:10.3762/bjoc.15.141

• in organic synthesis [1][2]. Such species can undergo different reactions, driven either by their carbanionic or carbenic behavior [3][4], thus leading to various products. In contrast, the transmetalation of lithiated oxiranes and the evolution of the resulting species have been less explored

• ]. Alternatively, Unemaya et al. and more recently Buchwald et al. described a Negishi cross coupling of aryl bromides or chlorides to α-CF3-oxiranyl zincates generated by lithiation of trifluoromethyloxirane and transmetalation with zinc chloride [10][11]. In this context and based on the pioneering work of

Diastereo- and enantioselective preparation of cyclopropanol derivatives

• Marwan Simaan and
• Ilan Marek

Beilstein J. Org. Chem. 2019, 15, 752–760, doi:10.3762/bjoc.15.71

• cyclopropylmagnesium species 6MgBr, the selective oxidation reaction of the copper species, resulting from a transmetalation reaction, was similarly achieved by reaction with oxenoid [71][79][80][86][87][88][89]. In all cases, cyclopropanols 7 were obtained as single diastereoisomer (dr 98:2:0:0) with excellent

Nucleofugal behavior of a β-shielded α-cyanovinyl carbanion

• Rudolf Knorr and
• Barbara Schmidt

Beilstein J. Org. Chem. 2018, 14, 3018–3024, doi:10.3762/bjoc.14.281

• acrylonitrile derivative 1 or by an Sn/Li transmetalation reaction of n-butyllithium (“n-BuLi”) with the α-stannyl derivative 3. Due to intermolecular LiN coordination, 2Li was deduced [4] to form a clustered ground state that showed no obvious rate anomaly with previously [4] studied electrophiles; this should

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

• transmetalation between D and AlMe3, with the concomitant regeneration of methyl-Co(I) A (step d). Carboxyzincation of alkynes The good reactivity and high functional-group compatibility of organozinc compounds render them as important reagents in organic synthesis [38][39]. For their preparation, direct and

• reduced to Co(I) (A) in the presence of metallic Zn. The oxidative cyclization of A with alkyne 16 and CO2 affords cobaltacycle B (step a). Next, the transmetalation between B and the Zn(II) species occurs, which affords the alkenylzinc intermediate C (step b) [41], which is then reduced with Zn powder

• formed (step a) [42]. Then, the insertion of CO2 into the Co–C(sp3) bond occurs, and the seven-membered Co intermediate C is obtained (step b). The transmetalation of C with the Zn(II) species proceeds then to afford the alkenylzinc species D (step c). The subsequent two-electron reduction of D with Zn

Some mechanistic aspects regarding the Suzuki–Miyaura reaction between selected ortho-substituted phenylboronic acids and 3,4,5-tribromo-2,6-dimethylpyridine

• Piotr Pomarański,
• Piotr Roszkowski,
• Jan K. Maurin,
• Armand Budzianowski and
• Zbigniew Czarnocki

Beilstein J. Org. Chem. 2018, 14, 2384–2393, doi:10.3762/bjoc.14.214

• with ortho-substituted phenylboronic acid for triaryl products. Summary of results for coupling with ortho-substituted phenylboronic acid for diaryl products. Proposed intermediates for the 1,2-addition of 5 with methoxy group. A) Oxidative addition step. B) Transmetalation step. Proposed intermediates

• for the 1,3-addition with methoxy group. A) Oxidative addition step. B) Transmetalation step. Proposed intermediates for the 1,2-addition with chlorine atom. A) Oxidative addition step. B) Transmetalation step. Proposed intermediates for the 1,3-addition with chlorine atom. A) Oxidative addition step

• . B) Transmetalation step. Optimization for the synthesis 6–9. Compound 10 was not detected in the mixture. Optimization of the synthesis of compounds 1–3. Rotational barriers of compounds 7 and 10. Optimization of the reaction conditions for the synthesis of 12–14. Optimization of the reaction