Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing

Martinez-Erro, Samuel (author): Stockholms universitet,Institutionen för organisk kemi

Sanz-Marco, Amparo (author): Stockholms universitet,Institutionen för organisk kemi

Bermejo Gómez, Antonio (author): Stockholms universitet,Institutionen för organisk kemi

Vazquez-Romero, Ana (author): Stockholms universitet,Institutionen för organisk kemi

Martín-Matute, Belén (author): Stockholms universitet,Institutionen för organisk kemi

(creator_code:org_t)

2016-09-30
2016
English.
In: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 138:40, s. 13408-13414

Related links:: https://doi.org/10.1...; show more...; https://doi.org/10.1...; https://su.diva-port... (primary) (Raw object); https://urn.kb.se/re...; https://doi.org/10.1...; https://urn.kb.se/re...; show less...

Abstract Subject headings

A mild base-catalyzed strategy for the isomerization of allylic alcohols and allylic ethers has been developed. Experimental and computational investigations indicate that transition metal catalysts are not required when basic additives are present. As in the case of using transition metals under basic conditions, the isomerization catalyzed solely by base also follows a stereospecific pathway. The reaction is initiated by a rate-limiting deprotonation. Formation of an intimate ion pair between an allylic anion and the conjugate acid of the base results in efficient transfer of chirality. Through this mechanism, stereochemical information contained in the allylic alcohols is transferred to the ketone products. The stereospecific isomerization is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioenriched (up to 97% ee) enol ethers.

By the author/editor: Martinez-Erro, S ...; Sanz-Marco, Ampa ...; Bermejo Gómez, A ...; Vazquez-Romero, ...; Ahlquist, Mårten ...; Martín-Matute, B ...

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Organic Chemistr ...

Kungliga biblioteket hanterar dina personuppgifter i enlighet med EU:s dataskyddsförordning (2018), GDPR. Läs mer om hur det funkar här.
Så här hanterar KB dina uppgifter vid användning av denna tjänst.