Journal
JOURNAL OF SULFUR CHEMISTRY
Volume 42, Issue 6, Pages 591-603Publisher
TAYLOR & FRANCIS LTD
DOI: 10.1080/17415993.2021.1971670
Keywords
Trialkylboranes; dithiane oxides; sulfoxide; thiolate anion; 1; 2-migration; displacement
Categories
Funding
- Cardiff University
- King Saud University [RSP-2021/404]
- University of Basrah
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In this study, various 2-substituted-1,3-dithiane oxides were metalated and reacted for the first time with a trialkylborane, leading to the migration of functional groups and the formation of novel products. However, the overall yields were low in these reactions.
Various 2-substituted-1,3-dithiane oxides (1-oxide and 1,3-dioxide) have been metalated and reacted for the first time with a trialkylborane (trioctylborane). The 2-chloro-1,3-dioxide results in migration of an octyl group from boron to carbon with the displacement of chloride and gives nonanoic acid after oxidation, but there is no evidence for a second migration involving displacement of a sulfenate group. The reaction involving lithiation of the 2-methoxy-1-oxide results in two migrations, with the displacement of both the methoxy group and the thiolate unit of the dithiane ring, giving dioctyl ketone after oxidation, but the yield is low, primarily because thiophilic addition of the lithiating agent predominates over lithiation. Again, there is no evidence for the displacement of the sulfenate unit. However, the intermediate prior to oxidation can be treated with trifluoroacetic anhydride to induce a Pummerer rearrangement, and the presumed trifluoroacetoxyalkylthiolate group then acts as a novel leaving group and is displaced, resulting in trioctylmethanol on oxidation, but the yield is again very low.
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