Interplay between the Directing Group and Multifunctional Acetate Ligand in Pd-Catalyzed anti-Acetoxylation of Unsymmetrical Dialkyl-Substituted Alkynes

• The cooperative action of the acetate ligand, the 2-pyridyl sulfonyl (SO2Py) directing group on the alkyne substrate,and the palladium catalyst has been shown to be crucial forcontrolling reactivity, regioselectivity, and stereoselectivity in theacetoxylation of unsymmetrical internal alkynes under mildreaction conditions. The corresponding alkenyl acetates wereobtained in good yields with complete levels of beta-regioselectivityandanti-acetoxypalladation stereocontrol. Experimental andcomputational analyses provide insight into the reasons behindthis delicate interplay between the ligand, directing group, and themetal in the reaction mechanism. In fact, these studies unveil themultiple important roles of the acetate ligand in the coordinationsphere at the Pd center: (i) it brings the acetic acid reagent into close proximity to the metal to allow the simultaneous activation ofthe alkyne and the acetic acid, (ii) it serves as an inner-sphere base while enhancing the nucleophilicity of the acid, and (iii) it acts asan intramolecular acid to facilitate protodemetalation and regeneration of the catalyst. Further insight into the origin of the observedregiocontrol is provided by the mapping of potential energy profiles and distortion-interaction analysis

Subject headings

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

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

Keyword

multifunctional ligand; ligand-assisted proton shuttle; acetoxylation of alkynes; unsymmetrical dialkyl alkynes; metal-ligand cooperativity; directing group

Publication and Content Type

ref (subject category)

art (subject category)