Base-Induced Sulfoxide-Sulfenate Rearrangement of 2-Sulfinyl Dienes for the Regio- and Stereoselective Synthesis of Enantioenriched Dienyl Diols

Velado, Marina; Martinović, Manuel; Alonso, Inés; Tortosa, Mariola; Fernández de la Pradilla, Roberto; Viso, Alma (2023) Base-Induced Sulfoxide-Sulfenate Rearrangement of 2-Sulfinyl Dienes for the Regio- and Stereoselective Synthesis of Enantioenriched Dienyl Diols. The Journal of Organic Chemistry, 88 (6). pp. 3697-3713. ISSN 0022-3263

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Abstract

The base-induced [2,3]-sigmatropic rearrangement of a series of enantiopure 2-sulfinyl dienes has been examined and optimized using a combination of NaH and iPrOH. The reaction takes place by allylic deprotonation of the 2-sulfinyl diene to give a bis-allylic sulfoxide anion intermediate that after protonation undergoes sulfoxide-sulfenate rearrangement. Different substitution at the starting 2-sulfinyl dienes has allowed us to study the rearrangement finding that a terminal allylic alcohol is determinant to achieve complete regioselectivity and high enantioselectivities (90:10–95:5) with the sulfoxide as the only element of stereocontrol. Density functional theory (DFT) calculations provide an interpretation of these results.

Item Type:	Article
Uncontrolled Keywords:	Column chromatography; Mixtures; Oxides; Rearrangement; Vinyl
Subjects:	NATURAL SCIENCES > Chemistry > Organic Chemistry
Divisions:	Division of Physical Chemistry
Depositing User:	Josipa Karadžole
Date Deposited:	11 Nov 2025 10:03
URI:	http://fulir.irb.hr/id/eprint/10190
DOI:	10.1021/acs.joc.2c02931

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