Base-induced rearrangements of mesityl thienyl sulfones

A truce on the Smiles rearrangement: revisiting an old reaction—the Truce–Smiles rearrangement

“…For example, it has been shown that substituted thienyl sulfones 15 (R = Me) undergo the Truce-Smiles rearrangement via an addition-elimination sequence to generate sulfinic acids 16, Scheme 7. 14 Here, the reaction proceeds via addition of the anion to the thiophene ring at position C-3, and not via a spiro-cyclic intermediate as usual.…”

“…[20][21][22] Over the course of the next 25 years or so, Truce went on to report the rearrangement of various o-methyl-diaryl sulfones into arylsulfinic acids in high yield. [10][11][12][13][14] It was found that only compounds with o-methyl groups underwent the rearrangement, however it has also been demonstrated that potassium tert-butoxide in DMSO is capable of effecting the rearrangement. 13 …”

“…In particular, the Smiles rearrangement is a reaction which has seen widespread use in organic chemistry, 9 however, a simple variant of this reaction-the Truce-Smiles rearrangementhas been little used in recent times, despite it arguably being more synthetically useful due to the selective formation of carbon-carbon (C-C) bonds, Scheme 1. [10][11][12][13][14][15][16] Traditionally, the definition of this particular variant follows two important differences to the more common Smiles rearrangement, these are: (1) a carbanion is the nucleophile rather than a heteroatom and (2) whereas the Smiles rearrangement requires an activating substituent in the migrating aryl unit (e.g. ortho or para-nitro groups), such activation is not needed, and perhaps would not be tolerated, in the Truce-Smiles rearrangement.…”

Synthesis and diatropicity of a trans-10c-methyl-10b,10c-dihydropyrene-containing cyclophane: a novel aromatic molecule with a (1,3)cyclophane within the π-cloud of a [14]annulene

“…An orange oil (30 mg) was obtained (Found: M+, 348.1877. C27H24 requires M, 348.1878); ;l,,,(cyclohexane)/nm 349, 368, 393 and 496; v,,,/cm-' 2920,2860, 1460,870,780 and 720; SH, see discussion in text; m/z 348 (M+, 12%), 333 (23), 229 (loo), 215 (41), 202 (lo), 149 (25), 131 (13) and 91 (21).…”

The Truce–Smiles rearrangement and related reactions: a review

“…The Truce research group reported 98 an attempted rearrangement of a thiophene substrate, which resulted in a product sug- gesting nucleophilic aromatic substitution at the ortho-position rather than the ipso-position of the migrating aryl ring. The product resulted from formation of the 1,2-adduct isomer (Fig.…”