0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via Dibutyl Hexanedioate by Dicarbonylation of Buta-1,3-diene

DOI: 10.1055/sos-SD-120-00173

Yang, Z.; Dong, K.Science of Synthesis Knowledge Updatesearly view.

Despite the developments in homogeneous catalytic carbonylation in the past 80 years, several aims were still to be achieved. Among them, the direct dicarbonylation of buta-1,3-diene to afford an adipate (hexanedioate) represents one of the most salient challenges. This process is a superior alternative to the nitric acid mediated oxidation of cyclohexanone, which requires an anti-corrosive reaction vessel and produces stoichiometric amounts of nitrous oxide (N2O). Beller and co-workers have presented a method for the palladium-catalyzed dicarbonylation of buta-1,3-diene that provides dialkyl adipates. The key to success is the choice of the ligand; the use of bidentate phosphine ligands featuring basic pyridyl substituents on phosphorus proved essential for high activity (e.g., ligand 26). By this protocol, the dialkoxycarbonylation of buta-1,3-diene with butan-1-ol led to the direct synthesis of adipate diesters (e.g., 27) in high yield and selectivity (Scheme 14).[‌18‌]

Meeeee 88 Meeeeee Meeeeee ee Meeeeeeeeeeeeee ee Meee-8,8-eeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeee Meeeeeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee. Me eeeee ee eeeeeeeeee ee eee eeeee, eeeeeee eeeeee eeeeeee. Meeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

M 8-eM eeeee-eee eeee eee eeeeeee eeee Me(M8MMM8)8 (8.8 eee%), eeeeee 88 (8.8 eee%), MeMM (8.8 eee%), eee ee eeee-eeeee eeeeeee eee. Mee eeee eee eeeeee ee e MMMM/eeeee eeeeee eeeeee (Meeeeee 88 ee Meeee) eee e eeeeeeee eee eee eeee eeeeeeeee eeee e eeeeee ee eee eeeeeeeeee. Mee eeee eee eeeeeeeee eeeee eeeeeee eeeeeeee eee eeeeeeeee eeee eeeee (8 ×). MeMM (8.8 eM) eee eeeeeeee ee eeeeeee, eee eeee e eeeeeeeeeeee eeeeeeee ee eeee-8,8-eeeee ee eeeeeee (8.8 eeee) eee eeeee ee eee eeeeeeee eeee, eeeee eee eeeee ee ee eeeee eeeee eee eee eeee e 888-eM Meee 8888 eeeeee eeeeeeeee eeeee eeeee. Me ee, eee eeeeeeeee eee eeeeeee eeee MM (8 ×) eee eeee eeeeeee eeee MM (88 eee). Mee eeeeeee eee eeeeee ee e eeeeeeeee eeeeeeeeeee eee 88 e. Meeeeeeeee, eee eeeeeeeee eee eeeeee ee ee eee eee eeeeeeee eee eeeeeeeee eeeeeeee. Meeeeeeeee (8.8 eeee) eee eeeee ee eee eeeeeee ee ee eeeeeeee eeeeeeee. M eeeeee ee eee eeeeeee eee eeeeeeee ee MM. Meee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 88:8); eeeee: 88%.