α-Arylation by Rearrangement : On the Reaction of Enolates with Diaryliodonium Salts

• Surprising equilibration: A new mechanism for the title reaction is supported by DFT calculations and experimental observations. The CI and OI intermediates are isoenergetic and equilibrate quickly. Thus, any chiral information induced in the initial complex will be destroyed. In the final CC bond-forming step, a [2,3]-rearrangement from the OI bonded intermediate is slightly preferred over the [1,2]-elimination from the CI bonded isomer (see scheme).

Subject headings

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

NATURVETENSKAP  -- Kemi -- Organisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Organic Chemistry (hsv//eng)

Keyword

arylation

density functional calculations

hypervalent compounds

iodanes

reaction mechanisms

Chemistry

Kemi

organisk kemi

Organic Chemistry

arylation • density functional calculations • hypervalent compounds • iodanes • reaction mechanisms

Publication and Content Type

ref (subject category)

art (subject category)