Saleh, Basil A., Smith, Keith, Elliott, Mark Christopher  ORCID: https://orcid.org/0000-0003-0132-0818, Jones, Dyfyr Heulyn, Kariuki, Benson M. ORCID: https://orcid.org/0000-0002-8658-3897 and El Hiti, Gamal A.
2016.
Reactions of organoboranes with carbanions bearing three potential leaving groups: unusual processes, products and mechanisms.
Tetrahedron
72
(44)
, pp. 6914-6928.
10.1016/j.tet.2016.09.005
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Abstract
Known reagents that transfer three alkyl groups of a trialkylborane intramolecularly to a single carbon atom lack features to influence stereochemistry. We have investigated four reagents of type LiCCl2X, where X might be amenable to variation. All behaved differently. With X=OR (R=cyclohexyl, menthyl), the reagent decomposed, leading to only low yields of triple migration products. With X=S(O)Ph, a single migration occurred, followed by isomerisation to boron enolate-like species that hydrolysed to α-chloroalkyl phenyl sulfoxides or reacted with aldehydes to aldol-like products. With X=SO2Ph, the major product was the corresponding α,α-dichloroalkyl phenyl sulfone, apparently formed through a redox reaction. With X=S(O)(NMe)Ph, products of three intramolecular alkyl migrations were obtained with unhindered trialkylboranes. Attempts have been made to gain understanding of the sulfoxide process by investigating proportions of aldol-like products, using X-ray crystallography and ab initio calculations.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry |
| Subjects: | Q Science > QD Chemistry |
| Uncontrolled Keywords: | Trialkylborane; Sulfoximine; Rearrangement; Sulfoxide; Sulfone |
| Publisher: | Elsevier |
| ISSN: | 0040-4020 |
| Funders: | EPSRC |
| Date of First Compliant Deposit: | 11 October 2016 |
| Date of Acceptance: | 5 September 2016 |
| Last Modified: | 14 Nov 2024 22:30 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/94970 |
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