Mechanism of reactions of sulphonium salts with organolithium reagents

Harrington, D. E.; Weston, John B.; Jacobus, John; Mislow, Kurt

doi:10.1039/c39720001079

Cited by 22 publications

(4 citation statements)

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“…The 'H n.m.r. spectrum of the products obtained in this experiment was consistent with that of a mixture authentic (8) and (9) and the cross-over products (2) and (13) were not detected at all. Reaction of(1) with BuLi.-To a stirred solution of (1) (188 mg, 0.87 mmol) in T H F (10 ml), BuLi (0.78 ml, 15% solution in hexane) was added under nitrogen at -72 "C in a dry iceacetone bath.…”

Section: Methodssupporting

confidence: 82%

Ligand coupling within σ-sulphurane intermediates formed in the reaction of benzyl 2-pyridyl and related sulphoxides with Grignard reagents

Ōae¹,

Kawai²,

Furukawa³

et al. 1987

J. Chem. Soc., Perkin Trans. 2

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c tro comm unica ti0 ns, C h of uga o ka, C h o f us hi, Tokyo 182, Japan The reaction of benzyl or 1 -phenylethyl 2-pyridyl sulphoxide (1) or (18) with a Grignard reagent was found to give the ligand-coupling product, i.e., 2-benzylpyridine or 2-(1 -phenylethyl)pyridine (2) or (22) in excellent yield. This coupling reaction was found to proceed within the o-sulphurane formed as an intermediate upon treatment of benzyl2-pyridyl and related sulphoxides with a Grignard reagent. The stereochemical course of this coupling reaction involves complete retention at the benzylic carbon.

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Section: Methodssupporting

confidence: 82%

Ligand coupling within σ-sulphurane intermediates formed in the reaction of benzyl 2-pyridyl and related sulphoxides with Grignard reagents

Ōae¹,

Kawai²,

Furukawa³

et al. 1987

J. Chem. Soc., Perkin Trans. 2

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show abstract

“…Ether was added to the concentrated liquors and the salt allowed to crystallize. The salt was isolated by vacuum filtration and recrystallized from methylene chloride-ether to yield 1.5 g (56%) of 5-(p-trifluoromethylphenyl)dibenzothiophenium fluoroborate (6d): mp 182-184°; ir (KBr) v 3106 (ArH), 1605 (aromatic), 1325 (sym CF3Ar), 1176 (asym CF3Ar), (BFr), 839 (para-disubst aromatic), 755 (aromatic), 704 (aromatic); uv ( ° 315 nm (e 3200), 270 (10,800), 243 (33,200), 235 (34,000); nmr (DMSO-4f) 7.49 (4 H, m) and 6.90 (8 H, m). Anal.…”

Section: Methodsmentioning

confidence: 99%

“…The organolithium was titrated for active organometallic with 0.1 N standard hydrochloric acid and found to be 0.8 M in active m-trifluoromethylphenyllithium. The organolithium was further characterized as its trimethylsilyl derivative by quenching an aliquot with excess trimethylchlorosilane: ir (CC14) 6), 204 (24), 203 (100), 76 (10). The results for the remaining organolithiums are summarized in Table V.…”

Section: Methodsmentioning

confidence: 99%

“…1242 (=COC-), 1031 (=COC-), 697 (aromatic); uv *° 283 nm (e 7300), 255 (11,400), 230 (21,572); nmr (CC14) 5 3.71 (3 H, s, CHaOAr), 6.7 (1/2 of AA'BB' pattern), 7.13 1166 (asym CF3Ar), 1129 (asym CF3Ar), 843 (para-disubst aromatic); uv X™H 292 nm U 520), 285 (1040), 280 (1040), 260 sh (7800), 250 (12,500), 238 sh (10,900), 215 sh (10,900); nmr (CC14) 5.30 (1 H, d,7 = 10 Hz, -HC=), 5.73(lH,d,/= 18Hz,-HC=), 6.70 (1 H, dd, J = 18, 10 Hz, ArCH=), 7.15-7.7 (4 H, m, ArH); mass spectrum m/e (70 eV) (rel intensity) 172.0478 (caled for C9H7F3, 172.04998) (100), 103 (17), 69 (26).…”

Section: Table V Preparation Of Organolithiumsmentioning

confidence: 99%

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