Thiophilic addition of phenyllithium to thiobenzophenone

Beak, Peter; Worley, Jimmy W.

doi:10.1021/ja00716a072

Cited by 43 publications

(11 citation statements)

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“…This reaction presents an alternative approach for the synthesis of 2,3-dicarbonylpyrrole derivatives. , In contrast with the construction of 88 , in the synthesis of 95 with N -methylprop-2-yn-1-amine as the amine component, the thiophilic nucleophilic reaction ,− for formation of thiiranium intermediate 98 , (also see Scheme ) should be critical for the formation of 95 via 1,2-acyl migration (Scheme ). …”

Section: Heteroannulation Reactions Via Ketene Ns-acetalsmentioning

confidence: 99%

Chemistry of Ketene N,S-Acetals: An Overview

et al. 2016

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Push-pull alkenes, which bear electron-donating and -accepting group(s) at both termini of a C═C double bond, respectively, are of interest not only for their unique electronic properties but also for their importance as versatile building blocks in organic synthesis. In the world of ketene acetals having the push-pull alkene skeleton, ketene N,S-acetal is most likely the biggest family according to the number and types of these compounds. The first ketene N,S-acetal compound was reported in 1956. As a cyclic ketene N,S-acetal compound, nithiazine, the first lead structure of neonicotinoid insecticides, was reported in 1978. The characteristics of ketene N,S-acetals, which have the structural feature of ketene S,S-acetals and enaminones, make them versatile and easy to use, especially in cyclization and multicomponent reactions for the synthesis of various heterocyclic systems and related natural products. There has been an increasing wealth of information about the synthesis and synthetic applications of ketene N,S-acetals, especially, in recent years. This review provides comprehensive knowledge on the chemistry of ketene N,S-acetals.

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Section: Heteroannulation Reactions Via Ketene Ns-acetalsmentioning

confidence: 99%

Chemistry of Ketene N,S-Acetals: An Overview

et al. 2016

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“…Reaction of exogenous phenyl-lithium 35 with the iodoisothiocyanate (1) at -78 "C for 25 min afforded a quantitative yield of N-(trans-2-iodocyclohexyl) thiobenzamide (21) but, as before, treatment of the product with potassium carbonate-acetone at 20 "C for 15 h effected cyclization to give 2-phenyl-cis-3a,4,5,6,7,7ahexahydrobenzothiazole (13). Although dialkylthioketens 36 and diaryl-37 and dialkyl-thioketones 38 have been shown to react with phenyl-lithium zia thiophilic addition, no product resulting from attack of the phenyl anion on the sulphur atom of the isothiocyanate group of the iodoisothiocyanate (1) was isolated. Moreover, no metal-halogen exchange between the substrate and phenyl-lithium was observed.…”

Section: Methodsmentioning

confidence: 99%

vic-Iodothiocyanates and iodoisothiocyanates. Part 4. The synthesis of 2-substituted-2-thiazolines

Cambie¹,

Chambers²,

Rutledge³

et al. 1981

J. Chem. Soc., Perkin Trans. 1

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The reactions of trans-1 -iodo-2-isothiocyanatocyclohexane with a number of carbon nucleophiles to form 2substituted-2-thiazolines are described. Reactions of several vic-iodoisothiocyanates with butyl-lithium give products which are dependent on the solvent and/or temperature.IN preceding papers we have reported methods for the conversion of vic-iodoisothiocyanates into thiazolidin-2ones,l 2-amino-2-thiazolines,l and 2-alkoxy-2-thiazolines.2 We report here reactions of a representative vic-iodoisothiocyanate (1), with a series of carbon nucleophiles to form 2-cyano-, 2-alkyl-, and 2-aryl-2thiazolines. The latter compounds are of synthetic value since protons on carbon atoms attached to C-2 of the thiazoline nucleus are acidic; use has been made of this property by Meyers and his co-workers in the synthesis of protected carbonyl compounds. For example, the labile P-hydroxyaldehyde (4) is formed when the litliio-thiazoline (5) is treated with cyclohexanone and the thiazolinyl moiety is removed subsequently by reduction and mercury(I1)-catalysed hydrolysis. Hackler and Balko recently reported the preparation of two 2-alkyl-2-thiazolines from the reaction of carbon nucleophiles with vic-chloro-and vic-bromo-isothiocyanates but their products were obtained in only moderate yields (35% and 42%). RESULTS AND DISCUSSION/ P C l t SCHEME 1 out by examination of the mass spectrum, which showed fragmentation peaks corresponding to the loss of C1, CH,Cl, and SCH,Cl from the molecular ion, but not to TABLE 1 Reactions of trans-l-iodo-2-isothiocyanatocyclohexane H RM KCN p-OMeC,H,CZCLi PhCrCLi Me,SiCXLi MeMgI EtMgI BuMgBr PhLi Some products were prepared by several modifications ; Isolated by p.1.c. the loss of CN, CH,CN, or SCH,CN. Moreover, the use of 13C n.m.r. substituent chemical-shift values allows differentiation between the structures (2) and (3); the combined a-effect of a carbon bearing a sulphur and chlorine atom would afford a chemical shift of ca. 6c 51 (C1= +31, SR = +20) (observed 6c 42.5) compared with a chemical shift of ca. aC 24 (SR = +20, CN = +4) for a carbon bearing a sulphur atom and a nitrile group. the yield quoted is the highest obtained. After distillation.

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“…[72] However, various other reactions such as carbophilic addition, reduction, double addition, and formation of ene sulfides proceed concurrently, thus greatly reducing the efficiencies of such reactions. On the contrary, additions of allylic Grignard reagents afford products derived from a direct carbophilic attack and a subsequent allylic shift.…”

Section: Regioselective Functionalization Of Thiocarbonyl Compounds Umentioning

confidence: 99%