CF₃SO₂X (X = Na, Cl) as reagents for trifluoromethylation, trifluoromethylsulfenyl-, -sulfinyl- and -sulfonylation and chlorination. Part 2: Use of CF₃SO₂Cl

• Hélène Chachignon,
• Hélène Guyon and
• Dominique Cahard

Beilstein J. Org. Chem. 2017, 13, 2800–2818, doi:10.3762/bjoc.13.273

• review. The direct introduction of CF3S and CF3S(O) motifs also occupies a prime position in this review. 1 Trifluoromethylation Csp3–CF3 bond-forming reactions Trifluoromethylation of silyl enol ethers and enol acetates: After their original reports on the trifluoromethylation of aromatics in 1990 (Csp2

• –CF3 bond-forming reactions; see later in the text, Scheme 24) [6][7], Kamigata and co-workers studied silyl enol ethers in 1997 in trifluoromethylation reactions. Kamigata’s group reported that in the presence of RuCl2(PPh3)3, in benzene at 120 °C, silyl enol ethers could furnish the corresponding α

• pathway that involved Ru(II)/Ru(III) metallic species (Scheme 1). The trifluoromethylation of silyl enol ethers can also be adressed in a continuous-flow procedure. To do so, the appropriate ketones were transformed in situ into the corresponding silyl enol ethers, which were then reacted with CF3SO2Cl in

New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

• Pavel Nagorny and
• Zhankui Sun

Beilstein J. Org. Chem. 2016, 12, 2834–2848, doi:10.3762/bjoc.12.283

• form the corresponding salts, and these generated in situ ion pairs were treated with silyl enol ethers in the presence of chiral catalysts L2–L4 to form chiral addition products. High levels of chirality transfer were generally observed for various 6-membered nitrogen-containing heterocyclic

• -methylpiperidinium iodide. Both L5 and L6 were found to promote the Mannich reaction between N-Troc-isoquinolinium chlorides and silyl enol ethers. Catalyst L6 with non-coordinating BArF− counterion was found to have a significantly higher activity than L5 with iodide counterion, probably, due to the competitive

Conjugate addition–enantioselective protonation reactions

• James P. Phelan and
• Jonathan A. Ellman

Beilstein J. Org. Chem. 2016, 12, 1203–1228, doi:10.3762/bjoc.12.116

• enol ethers [20][21]. Electron-rich and neutral indoles were efficient substrates for the reaction; however, electron-poor indoles showed attenuated reactivity even when 1.6 equivalents of SnCl4 were employed (60–63% yield, 96:4 to 96.5:3.5 er). Indoles lacking substitution at the 2-position (R1 = H

• catalytic (R)-3,3’-dibromo-BINOL (16) and stoichiometric SnCl4 [19] (Scheme 4). The authors proposed that complex 18 acted as a chiral proton source to protonate a tin-enolate intermediate based upon related complexes that the Yamamoto group had previously used for the enantioselective protonation of silyl

Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

• Barry M. Trost,
• Michael C. Ryan and
• Meera Rao

Beilstein J. Org. Chem. 2016, 12, 1136–1152, doi:10.3762/bjoc.12.110

• tolerate many sensitive functional groups, such as free alcohols, silyl enol ethers, and ketones, which makes it an attractive metal for late stage functionalization and elaboration of complex molecules. It is thought that the origin of ruthenium’s divergent behavior stems from a difference in reaction

Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update

• Bin Yu,
• Hui Xing,
• De-Quan Yu and
• Hong-Min Liu

Beilstein J. Org. Chem. 2016, 12, 1000–1039, doi:10.3762/bjoc.12.98

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

• Katherine M. Byrd

Beilstein J. Org. Chem. 2015, 11, 530–562, doi:10.3762/bjoc.11.60

• This section will focus on Lewis acid-catalyzed ECA reactions, which employ stabilized nucleophiles such as silyl enol ethers and amines. Chiral Lewis acids play a dual role in these reactions. They activate the Michael acceptors by coordinating with the carbonyl oxygen and they provide a chiral

Efficient carbon-Ferrier rearrangement on glycals mediated by ceric ammonium nitrate: Application to the synthesis of 2-deoxy-2-amino-C-glycoside

• Alafia A. Ansari,
• Y. Suman Reddy and
• Yashwant D. Vankar

Beilstein J. Org. Chem. 2014, 10, 300–306, doi:10.3762/bjoc.10.27

• synthesis of C-glycosides [12][13][14]. Among these, the Ferrier rearrangement [15] of glycals with protic acids [5][16][17] or Lewis acids [18][19][20][21][22] and carbon nucleophiles such as allylsilanes [23], silylacetylenes [24], silyl enol ethers [25], olefins [26], and organozinc reagents [27] has

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

• Sebastian Krüger and
• Tanja Gaich

Beilstein J. Org. Chem. 2014, 10, 163–193, doi:10.3762/bjoc.10.14

• cycloheptadiene 265 via 264 in good yields. Further contributions to the topic have been put forward by the group of Echavarren [207] and Gung [208]. Cycloisomerization involving DVCPR Iwasawa and coworkers [209] discovered a cyclopropanation/DVCPR sequence of alkyne-substituted silyl enol ethers (for example 274

Gold(I)-catalyzed domino cyclization for the synthesis of polyaromatic heterocycles

• Mathieu Morin,
• Patrick Levesque and
• Louis Barriault

Beilstein J. Org. Chem. 2013, 9, 2625–2628, doi:10.3762/bjoc.9.297

• cyclizations of the enol ether 11a (R1 = p-BrC6H4, R2 = H) gave the corresponding benzothiophene 12a in 83% yield. The use of electron-poor silyl enol ether 11b (R1 = p-NO2C6H4, R2 = H) gave the desired product 12b, albeit in lower yield of 63%. Di- and trisubstituted silyl enol ethers 11c (R1 and R2 = H) and

Mechanistic studies on the CAN-mediated intramolecular cyclization of δ-aryl-β-dicarbonyl compounds

• Brian M. Casey,
• Dhandapani V. Sadasivam and
• Robert A. Flowers II

Beilstein J. Org. Chem. 2013, 9, 1472–1479, doi:10.3762/bjoc.9.167

• oxidation of several β-diketones and their related silyl enol ethers by CAN and the more lipophilic ceric tetra-n-butylammonium nitrate (CTAN) were measured in MeOH, MeCN and CH2Cl2 by using stopped-flow spectrophotometry [16]. In these experiments, initial oxidation of substrates generated radical cation

Tandem dinucleophilic cyclization of cyclohexane-1,3-diones with pyridinium salts

• Mostafa Kiamehr,
• Firouz Matloubi Moghaddam,
• Satenik Mkrtchyan,
• Volodymyr Semeniuchenko,
• Linda Supe,
• Alexander Villinger,
• Peter Langer and
• Viktor O. Iaroshenko

Beilstein J. Org. Chem. 2013, 9, 1119–1126, doi:10.3762/bjoc.9.124

• dielectrophiles has been a major research subject in both our laboratories. For example, we have studied reactions of quinolinium [36][37], isoquinolinium [38][39][40], quinazolinium [41][42] and quinoxalinium [43] salts with 1,3-bis(silyl enol ethers), i.e., masked 1,3-dicarbonyl compounds, which provided facile

• , which are subsequently cyclized by the addition of acid). In some cases the cyclization step failed, e.g., the reaction of 1,3-bis(silyl enol ethers) with pyridine in the presence of methyl chloroformate resulted in the formation of 1,4-dihydropyridines, which however, could not be cyclized by the

Asymmetric organocatalytic decarboxylative Mannich reaction using β-keto acids: A new protocol for the synthesis of chiral β-amino ketones

• Chunhui Jiang,
• Fangrui Zhong and
• Yixin Lu

Beilstein J. Org. Chem. 2012, 8, 1279–1283, doi:10.3762/bjoc.8.144

• few decades [7]. Among them, the Mukaiyama–Mannich reaction performed with silyl enol ethers and sulfonyl aldimines, catalyzed by a chiral Lewis acid complex, is one of the most important synthetic methods [8][9][10][11][12][13]. Apparently, direct use of inactivated ketones as a donor would be of

Facile isomerization of silyl enol ethers catalyzed by triflic imide and its application to one-pot isomerization–(2 + 2) cycloaddition

• Kazato Inanaga,
• Yu Ogawa,
• Yuuki Nagamoto,
• Akihiro Daigaku,
• Hidetoshi Tokuyama,
• Yoshiji Takemoto and
• Kiyosei Takasu

Beilstein J. Org. Chem. 2012, 8, 658–661, doi:10.3762/bjoc.8.73

• , Japan 10.3762/bjoc.8.73 Abstract A triflic imide (Tf2NH) catalyzed isomerization of kinetically favourable silyl enol ethers into thermodynamically stable ones was developed. We also demonstrated a one-pot catalytic reaction consisting of (2 + 2) cycloaddition and isomerization. In the reaction

• sequence, Tf2NH catalyzes both of the reactions. Keywords: isomerization; one-pot reaction; organocatalysis; silyl enol ethers; triflic imide; Introduction Silyl enol ethers, which are isolable equivalents of metal enolates, are useful and important intermediates in synthetic chemistry [1][2][3]. They

• react as a good nucleophile for the introduction of a carbon skeleton or a functional group at the α-position of a carbonyl group under appropriate conditions. Although silyl enol ethers are easily prepared from the corresponding ketones, the regiochemical issue would arise in the case of asymmetric

Recent developments in gold-catalyzed cycloaddition reactions

• Fernando López and
• José L. Mascareñas

Beilstein J. Org. Chem. 2011, 7, 1075–1094, doi:10.3762/bjoc.7.124

• (VIII) that participate in (4 + 2) annulations with polarized alkenes such as indoles, carbonyls, imines or silyl enol ethers [45]. Thus, different types of 6-membered carbocycles and heterocycles were prepared in good yields and notable regioselectivities. An example of these annulations, using indoles

Intramolecular hydroamination of alkynic sulfonamides catalyzed by a gold–triethynylphosphine complex: Construction of azepine frameworks by 7-exo-dig cyclization

• Hideto Ito,
• Tomoya Harada,
• Hirohisa Ohmiya and
• Masaya Sawamura

Beilstein J. Org. Chem. 2011, 7, 951–959, doi:10.3762/bjoc.7.106

• enhancement. Recently, we further developed the gold(I)-catalyzed 7-exo-dig cyclization of acetylenic silyl enol ethers with L1 [57]. In this context, we expected that the use of L1 as a ligand in the gold-catalyzed intramolecular hydroamination of alkynes would enable the construction of nitrogen-containing

Synthetic applications of gold-catalyzed ring expansions

• David Garayalde and
• Cristina Nevado

Beilstein J. Org. Chem. 2011, 7, 767–780, doi:10.3762/bjoc.7.87

• . Upon coordination of the metal to the alkyne 59, the 1,4-dipole 61 can be formed from oxocarbenium 60. Carbonyl compounds and carbonyl derivatives, such as imines or silyl enol ethers, can also be used as dipolarophiles to generate bicyclic furans 62 in fairly good yields (Scheme 20, reaction 2

Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters

• Haruo Aikawa,
• Tetsuro Kaneko,
• Naoki Asao and
• Yoshinori Yamamoto

Beilstein J. Org. Chem. 2011, 7, 648–652, doi:10.3762/bjoc.7.76

• Research, Tohoku University, Sendai 980-8578, Japan 10.3762/bjoc.7.76 Abstract Unprecedented alkylation of silyl enol ethers has been developed by the use of ortho-alkynylbenzoic acid alkyl esters as alkylating agents in the presence of a gold catalyst. The reaction probably proceeds through the gold

• -induced in situ construction of leaving groups and subsequent nucleophilic attack on the silyl enol ethers. The generated leaving compound abstracts a proton to regenerate the silyl enol ether structure. Keywords: alkylation; gold catalysis; leaving group; silyl enol ether; substitution reaction

• ; Findings Silyl enol ethers have been widely used in organic synthesis as effective carbon nucleophiles for the construction of carbon frameworks [1][2][3][4]. Generally, they react with a variety of electrophiles to give carbonyl compounds as products due to cleavage of the silicon–oxygen bond. For example

Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective

• Norio Shibata,
• Andrej Matsnev and
• Dominique Cahard

Beilstein J. Org. Chem. 2010, 6, No. 65, doi:10.3762/bjoc.6.65

• conditions to give ortho-trifluoromethylated arenes in good yields (Scheme 7). Togni’s reagent (37, see later in the text) could be used for this reaction, although product yields were as low as 11%. The reaction conditions for trifluoromethylation of silyl enol ethers and β-ketoesters were reinvestigated by

• -substituted α-trifluoromethyl β-ketoesters in good to excellent yields. In a second approach, 5 and tetrabutylammonium difluorotriphenylstannate were used for efficient electrophilic trifluoromethylation of various silyl enol ethers to give the corresponding α-trifluoromethyl ketones in good to high yields

• a bridged oxygen. Reactivity of (trifluoromethyl)dibenzochalcogenium salts. Pd(II)-Catalyzed ortho-trifluoromethylation of heterocycle-substituted arenes by Umemoto’s reagents. Mild electrophilic trifluoromethylation of β-ketoesters and silyl enol ethers. Enantioselective electrophilic

Fused bicyclic piperidines and dihydropyridines by dearomatising cyclisation of the enolates of nicotinyl-substituted esters and ketones

• Heloise Brice,
• Jonathan Clayden and
• Stuart D. Hamilton

Beilstein J. Org. Chem. 2010, 6, No. 22, doi:10.3762/bjoc.6.22

• it into a silyl enol ether 9. Silyl enol ethers and ketene acetals are known to add effectively to pyridinium species in an intermolecular manner [42][43][44][45][46]. Thus 7 was converted to silyl enol ether 9 in excellent yield under standard conditions. A single geometrical isomer was obtained

A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis

• Magnus Rueping and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2010, 6, No. 6, doi:10.3762/bjoc.6.6

• ]. In addition to arenes and heteroarenes, other nucleophiles including allylsilane, tosylamine, TMS-cyanide, acetylacetonates and silyl enol ethers were successfully used as nucleophilic components giving the substituted 3-phenylbutanoates 112 in high yields and with excellent diastereoselectivities

• (Scheme 41). The reaction could be performed at ambient temperatures and in sharp contrast to the previous described HBF4-mediated procedure, high anti-selectivity was observed in the formation of 112. Similar methods using silyl enol ethers were subsequently developed involving Bi(OTf)3 as Lewis acid

• catalyst [117][118]. While bismuth-catalyzed arylation of benzyl alcohols proceeded only at temperatures between 55 and 100 °C, the reaction of p-methoxybenzyl acetates 113 with silyl enol ethers 114 took place even at ambient temperatures to give the desired products 115 (Scheme 42) [118]. Again different

End game strategies towards the total synthesis of vibsanin E, 3-hydroxyvibsanin E, furanovibsanin A, and 3-O-methylfuranovibsanin A

• Brett D. Schwartz,
• Craig M. Williams and
• Paul V. Bernhardt

Beilstein J. Org. Chem. 2008, 4, No. 34, doi:10.3762/bjoc.4.34

• procedure based on the epoxidation of silyl enol ethers. Ketone 23 was smoothly converted into the TBS enol ether 27 (85% yield) with TBS triflate, which was then treated with dimethyldioxirane (DMDO). When work up was restricted to a simple 1 M hydrochloric acid wash (i.e. separatory funnel) only the

• oxidation on diketone 40, but to first protect the ketone functionality as silyl enol ethers as was undertaken in Scheme 7 (i.e. 27–48). Treating diketone 40 with t-butyldimethylsilyl trifluoromethanesulfonate afforded only the monoprotected product 53 (crude yield 55%), which smoothly underwent reduction