Fast and Highly Chemoselective Alkynylation of Thiols with Hypervalent Iodine Reagents Enabled through a Low Energy Barrier Concerted Mechanism.

Frei, Reto; Wodrich, Matthew D.; Hari, Durga Prasad; Borin, Pierre-Antoine; Chauvier, Clément; Waser, Jérôme (2014). Fast and Highly Chemoselective Alkynylation of Thiols with Hypervalent Iodine Reagents Enabled through a Low Energy Barrier Concerted Mechanism. Journal of the American Chemical Society, 136(47), pp. 16563-16573. American Chemical Society (ACS) 10.1021/ja5083014

[img]
Preview
Text
Fast and Highly Chemoselective Alkynylation of Thiols with Hypervalent Iodine Reagents Enabled through a Low Energy Barrier Concerted Mechanism..pdf - Published Version
Available under License Creative Commons: Attribution-Noncommercial (CC-BY-NC).

Download (2MB) | Preview

Among all functional groups, alkynes occupy a privileged position in synthetic and medicinal chemistry, chemical biology, and materials science. Thioalkynes, in particular, are highly useful, as they combine the enhanced reactivity of the triple bond with a sulfur atom frequently encountered in bioactive compounds and materials. Nevertheless, general methods to access these compounds are lacking. In this article, we describe the mechanism and full scope of the alkynylation of thiols using ethynyl benziodoxolone (EBX) hypervalent iodine reagents. Computations led to the discovery of a new, three-atom concerted transition state with a very low energy barrier, which rationalizes the high reaction rate. On the basis of this result, the scope of the reaction was extended to the synthesis of aryl- and alkyl-substituted alkynes containing a broad range of functional groups. New sulfur nucleophiles such as thioglycosides, thioacids, and sodium hydrogen sulfide were also alkynylated successfully to lead to the most general and practical method yet reported for the synthesis of thioalkynes.

Item Type:

Journal Article (Original Article)

Division/Institute:

School of Architecture, Wood and Civil Engineering

Name:

Frei, Reto;
Wodrich, Matthew D.;
Hari, Durga Prasad;
Borin, Pierre-Antoine;
Chauvier, Clément and
Waser, Jérôme

ISSN:

0002-7863

Publisher:

American Chemical Society (ACS)

Language:

English

Submitter:

Admin import user

Date Deposited:

18 Dec 2019 13:48

Last Modified:

03 May 2021 09:49

Publisher DOI:

10.1021/ja5083014

ARBOR DOI:

10.24451/arbor.5689

URI:

https://arbor.bfh.ch/id/eprint/5689

Actions (login required)

View Item View Item
Provide Feedback