Jump to main content
Jump to site search

Issue 6, 2015
Previous Article Next Article

Can acyclic conformational control be achieved via a sulfur–fluorine gauche effect?

Author affiliations

Abstract

The gauche conformation of the 1,2-difluoroethane motif is known to involve stabilising hyperconjugative interactions between donor (bonding, σC–H) and acceptor (antibonding, σ*C–F) orbitals. This model rationalises the generic conformational preference of F–Cβ–Cα–X systems (ϕFCCX ≈ 60°), where X is an electron deficient substituent containing a Period 2 atom. Little is known about the corresponding Period 3 systems, such as sulfur and phosphorus, where multiple oxidation states are possible. Conformational analyses of β-fluorosulfides, -sulfoxides and -sulfones are disclosed here, thus extending the scope of the fluorine gauche effect to the 3rd Period (F–C–C–S(O)n; ϕFCCS ≈ 60°). Synergy between experiment and computation has revealed that the gauche effect is only pronounced in structures bearing an electropositive vicinal sulfur atom (S+–O, SO2).

Graphical abstract: Can acyclic conformational control be achieved via a sulfur–fluorine gauche effect?

Back to tab navigation

Supplementary files

Article information


Submitted
10 Mar 2015
Accepted
16 Apr 2015
First published
17 Apr 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 3565-3571
Article type
Edge Article
Author version available

Can acyclic conformational control be achieved via a sulfur–fluorine gauche effect?

C. Thiehoff, M. C. Holland, C. Daniliuc, K. N. Houk and R. Gilmour, Chem. Sci., 2015, 6, 3565 DOI: 10.1039/C5SC00871A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements