Carbonylative Addition of Arylboronic Acids to Terminal Alkynes: A New Catalytic Access to α,β‐Unsaturated Ketones

Abstract

The carbonylative addition of arylboronic acids to terminal alkynes under mild conditions affords (E)-a,b-unsaturated ketones with good yields. The reaction was achieved with chloro(1,5-cyclooctadiene)rhodium(I) dimer or chlorodicarbonylrhodium(I) dimer as catalytic precursor without additional phosphine as their use inhibits the reaction. Experiments using deuterated 1-hexyne discarded the possibility of a rhodium-vinylidene intermediate, thus a catalytic cycle involving a 1,2-insertion of the terminal alkyne in a rhodium-acyl bond is proposed. This new reaction represents the first example of the hydroacylation of terminal alkynes involving rhodiumacyl reagents generated under CO pressure and promises a wide field of interest.

Deuteration of terminal alkynes realizes simultaneous live cell Raman imaging of similar alkyne-tagged biomolecules

“…The H/D or D/H exchange of terminal alkynes was dependent on its structure (whether conjugated or non-conjugated), pH (pD), and temperature. Furthermore, deuterated compounds are widely used in various research fields (e.g., synthetic chemistry, pharmaceutical science, and materials science) and the D-alkyne functional group is valuable for the synthesis of other deuterated functional groups, such as D-alkenes or D-alkanes, 13,27-29 D-ketones, 30 and D-aromatics. 31 Our findings related to D/H exchange of terminal alkynes provide further insights for the synthesis of D-labeled compounds using D-alkynes.…”

Organometallic catalysis: From concepts to selected applications

“…Using very similar reaction conditions, the carbonylative addition of arylboronic acids to butyl acrylate or acrolein affords the corresponding ketoester or ketoaldehydes with modest yields. The reaction could be enlarged to alkyne containing derivatives [37]. The first successful experiments were made with 1-hexyne 14 as model reagent.…”

Copper(I)-Catalyzed Synthesis of 2,5-Disubstituted Furans and Thiophenes from Haloalkynes or 1,3-Diynes

“…The discovery of new activation processes and selective transition-metal-catalyzed transformations of alkyne have significantly contributed to this field (Scheme 1). 6 While these protocols represent stalwart advances in the preparation of 2,5-disubstituted furans, there are still opportunities to design methods with more easily accessible materials and routines.…”