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. 2022 Apr 12:18:420-428.
doi: 10.3762/bjoc.18.44. eCollection 2022.

Cs2CO3-Promoted reaction of tertiary bromopropargylic alcohols and phenols in DMF: a novel approach to α-phenoxyketones

Ol'ga G Volostnykh  1 , Olesya A Shemyakina  1 , Anton V Stepanov  1 , Igor' A Ushakov  1
Affiliations

Cs2CO3-Promoted reaction of tertiary bromopropargylic alcohols and phenols in DMF: a novel approach to α-phenoxyketones

Ol'ga G Volostnykh et al. Beilstein J Org Chem. .

Abstract

The reaction of bromopropargylic alcohols with phenols in the presence of Cs2CO3/DMF affords α-phenoxy-α'-hydroxyketones (1:1 adducts) and α,α-diphenoxyketones (1:2 adducts) in up to 92% and 24% yields, respectively. Both products are formed via ring opening of the same intermediates, 1,3-dioxolan-2-ones, generated in situ from bromopropargylic alcohols and Cs2CO3.

Keywords: 1,3-dioxolan-2-one; acetylenic alcohol; bromoacetylene; phenols; phenoxyketone.

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Figures

Scheme 1
Scheme 1
Scope of the reaction of bromopropargylic alcohol 1a and phenols 2b–i.
Scheme 2
Scheme 2
Reaction of bromopropargylic alcohol 1b and phenols 2a and 2d.
Scheme 3
Scheme 3
Reaction of bromopropargylic alcohol 1c and phenol (2a).
Scheme 4
Scheme 4
Reaction of chloropropargylic alcohol and phenol (2a).
Scheme 5
Scheme 5
Reaction of bromopropargylic alcohol 1a and anilines.
Scheme 6
Scheme 6
Control experiments.
Scheme 7
Scheme 7
A plausible mechanism for the formation of phenoxyhydroxyketone 4.
Scheme 8
Scheme 8
A plausible mechanism for the formation of diphenoxyketone 5.
Scheme 9
Scheme 9
Examples of representative preparation of phenoxyketones 4.
Scheme 10
Scheme 10
α-Ketol rearrangement of phenoxyketones 4a and 4f.
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