Nucleophilic substitution at tricoordinate sulfur

Tillett, J. G.

doi:10.1021/cr60304a004

Cited by 92 publications

(33 citation statements)

References 81 publications

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“…(5.19) and (5.20) and the intermediate structures LXIc and LXIIc expected to be formed on these paths are compatible with the stereochemical outcome of the substitution reaction associated with the inversion of the pyramidal bond configuration at tricoordinate sulfur and phosphorus centers. Such a stereochemical outcome was obtained experimentally in reactions of various sulfinyl [177] and phosphinyl [178] derivatives.…”

Section: Substitution At Tricoordinate Sulfur and Phosphorus Centersmentioning

confidence: 80%

Quantum Chemistry of Organic Compounds

Минкин¹,

Simkin²,

Minyaev³

1990

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Section: Substitution At Tricoordinate Sulfur and Phosphorus Centersmentioning

confidence: 80%

Quantum Chemistry of Organic Compounds

Минкин¹,

Simkin²,

Minyaev³

1990

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“…The organic chemistry of SO 2 has been limited to the formation of arenesulfinic acids (Friedel-Crafts sulfinylation [1,2]), the copolymerization of SO 2 with alkenes or alkynes (polysulfone synthesis [3][4][5]), the synthesis of sulfinates by reaction with organometallic compounds [6][7][8], the ring-opening of oxiranes and oxetanes [8,9] leading to polysulfites [8,[10][11][12], the synthesis of sulfones [8,[13][14][15], the isomerization of alkenes via ene reaction/sigmatropic shift/retro-ene elimination sequence [16][17][18][19][20][21][22], and the cheletropic additions of conjugated polyenes [23][24][25] forming cyclic sulfones, as the [ω2s+π4s] ad-dition of SO 2 to isoprene producing 2,5-dihydro-3-methylthiophene-1,1-dioxide (sulfolene), a reaction known since 1914 [26,27].…”

Section: Introductionmentioning

confidence: 99%

Use of sultines in the asymmetric synthesis of polypropionate antibiotics

Vogel

Turks

Bouchez

et al. 2008

Pure and Applied Chemistry

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At low temperature and in the presence of an acid catalyst, SO 2 adds to 1,3-dienes equilibrating with the corresponding 3,6-dihydro-1,2-oxathiin-2-oxides (sultines). These compounds are unstable above -60°C and equilibrate with the more stable 2,5-dihydrothiophene 1,1-dioxides (sulfolenes). The hetero-Diels-Alder additions of SO 2 are suprafacial and follow the Alder endo rule. The sultines derived from 1-oxy-substituted and 1,3-dioxydisubstituted 1,3-dienes cannot be observed at -100°C but are believed to be formed faster than the corresponding sulfolenes. In the presence of acid catalysts, the 6-oxy-substituted sultines equilibrate with zwitterionic species that react with electron-rich alkenes such as enoxysilanes and allylsilanes, generating β,γ-unsaturated silyl sulfinates that can be desilylated and desulfinylated to generate polypropionate fragments containing up to three contiguous stereogenic centers and an (E)-alkene unit. Alternatively, the silyl sulfinates can be reacted with electrophiles to generate polyfunctional sulfones (one-pot, four-component synthesis of sulfones), or oxidized into sulfonyl chlorides and reacted with amines, then realizing a one-pot, four-component synthesis of polyfunctional sulfonamides. Using enantiomerically enriched dienes such as 1-[(R)-or 1-(S)-phenylethyloxy]-2-methyl-(E,E)-penta-1,3-dien-3-yl isobutyrate, derived from inexpensive (R)-or (S)-1-phenylethanol, enantiomerically enriched stereotriads are obtained in one-pot operations. The latter are ready for further chain elongation. This has permitted the development of expeditious total asymmetric syntheses of important natural products of biological interest such as the baconipyrones, rifamycin S, and apoptolidin A.

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“…[44,45] In this case, the reaction involves the attack of the organolithium reagent on the sulfur atom of the sulfoxide to generate a pentacoordinate σ-sulfurane 27, with the sulfur atom in the center of a trigonal bypyramid. [46] By way of a pseudorotation process different complexes can be formed, with the ligands occupying equatorial and apical positions (e.g., 28, 29). The complex that has the most electronegative group (G) occupying the apical position is the most stable and the one that undergoes bond rupture to generate the anion.…”

Section: Mechanistic Considerationsmentioning

confidence: 99%