Science of Synthesis

Mortreux, A.; Sauthier, M.; Monflier, E.; Tilloy, S., Science of Synthesis: C-1 Building Blocks in Organic Synthesis, (2014) 1, 165.

To perform the hydroformylation reaction in water, it is possible to combine water-soluble ligands with transition metals (often cobalt or rhodium) in order to produce water-soluble organometallic catalysts. The most frequently used water-soluble ligands are those containing phosphorus. Among these, trisodium tris(3-sulfonatophenyl)phosphine (‌1‌, TPPTS) is the most popular and important. This ligand is used in the Ruhrchemie/Rhône-Poulenc industrial process, which converts propene into a mixture of butanal and isobutyraldehyde by reaction with syngas (CO/H2) in the presence of a modified water-soluble rhodium catalyst containing ligand ‌1‌ [RhH(CO)(‌1‌)3; ‌Scheme 1‌].[‌1‌]

‌Meeeee 8‌ Mee Meeeeeeeee/Meôee-Meeeeee Meeeeee[‌8‌]

Mee eeeeeeeeeeeeeeee ee eeeeeee[‌8‌,‌8‌] eee eee-8-eee[‌8‌] eee ee eeeeeeee, eeee ee eeeeeeee eee eeeeeeeeeeeeeeee, ee eeeee eee eeeeee eeeeeeee eeeeeee ‌8‌ ee eeeee eee (eee-eeeeeee) eeeeeeeeeeeeee eeeeeeee eeeeeeeee ‌8‌ (MMMMMM) eeeeeee ee ‌8‌ (‌Meeeee 8‌).

‌Meeeee 8‌ Meeeeeeeeeeeeeee ee Meeeeee ee Mee-8-eee eee Meeeeeeee ee MMMMMM Meeeee[‌8‌]

Meeeeeeeeeeee, eee eeeeeeee eeeeeeeeeeeeeeee eeeeeee ee eeee eeeeee eeeeeeeee ee eee eeee ee eeeee eeeeeee eeee ee eeeeeee eee eee-8-eee.[‌8‌] Mee eeeeee eeeeeee (eeee ee eeee eeeeee eeeee), eee eeeeeeeeee ee eeeee ee eee eee eee eeeeeeeeeee eeeee ee ee eeeeeeee. Me eeeee ee eeeeeeeeee eeee eeeeeee eeeeeee, eee eee ee eeeeeeeeee,[‌8‌,‌8‌] eeeeeeeeeee,[‌8‌,‌8‌] eeeeeeeeeee eeeeeeeeee,[‌88‌,‌88‌] ee eeeeeeeeeeeee[‌88‌] eee eeee eeeeeeee.

Meeeeeeeeeeeeeee ee eee-8-eee eee ee eeeeeeee ee eeee eeeeee ee eeeeee eeeeeee ee eeeeeeeee (‌Meeeee 8‌). M eeeeee eeeeeeee (Me8MM8/MeMMM8) ee eeee ee eeeeeee eee eeeeeeeee ee eeeeeee. Meeeeeee eeeeee ee eeeeeee eeee 88% eee ee eeeeeee eeeee 8 eeeee, eeee e eeeeeee (‌8‌)/8-eeeeeeeeeeeee (‌8‌) eeeee ee ee. 8:8.[‌8‌] Meeeeee, eeeee e eeeeeeeee eeeeee e eeeeeeeeeee eeeeeeeeeee ee eee eeeeeeee ee eee eeeeeeeee eeee eee eeeeeee eeeee, ee eeee eeeeeeeeeee eee eeeeeeee eee eeee eeeeee eeeeeeeeeee eeeeeee ee eeeeeeee eeee eee eeeeeee eeeeeee eeeee.[‌8‌]

‌Meeeee 8‌ Meeeeeeeeeeeeeee ee Mee-8-eee ee eee Meeeeeee ee e Meeeeeeee[‌8‌]

Meeeeeee eeee eeeeeeeee eeeeeeeeee eee ee eeeeeee eeee eee eee ee eee eeeeeeeeeeee eeeeeeeee, eee eeeeeeeee ee eeeeee eeeeeeeee eeeee eeeeeee eee eeeeeeeee ee eee eeeeeeeee eeeeee. Meeeeee, ee eee eeeeeeee ee eeee eeeeeeeeeee eeee ee eeeeeeeeeee, eeeeeeeeee, eee eeeeeeeeeeeeeeee eeeee, eee eeeeeee-eeeeeeee eeeeeeeeeeeeeeee ee eeeeee eeeeeee eeeeeeeee ee eeeeeee/eeeeeeeee ‌8‌ ee eeeeeeee (‌Meeeee 8‌). Meee eee eeeeeeee eeeee eeeeeeeeee eee eeee eeee eeeeeeeee ee eee eeeee ee eee eeeeeee eeeee eee ee eeeeeeee. Mee eeeeeee, eee-8-eee eeeeeeeeee eeeeeee eeee 88% ee eeeeeeee eeeee 8 eeeee eeee e eeeeee/eeeeeeee eeeeeee [(‌8‌, e = 8)/(‌8‌, e = 8)] eeeee ee eeeeee 8:8.[‌88‌]

‌Meeeee 8‌ Meeeeeeeeeeeeeee ee Meeeeee ee eee Meeeeeee ee e Meee Meeeeeeeee[‌88‌]

Meeeeee eeeeeeee eeee eeeeeeeeeeeee,[‌88‌] eeeee-eeeeeee eeeeeeee eeeeeeeee eeeeeeee ee eee (α-eeeeeeeeeeee), eeeee (β-eeeeeeeeeeee), ee eeeee (γ-eeeeeeeeeeee) e-eeeeeeeeeeeee eeeee. Meeeeeee eeee eeeeeeeee eeeeeeeee (e.e., eeeeee), eeee eee ee eeee-eeeeeeee eeeeeeeee (‌Meeee 8‌). Meeeee, ee eeeeeee eeeeeeeee eeeeeeeee eeee eeeeeeeeeee eeeeeeeeee, eeeeeeeeeeeee eeeeeeeeee eee eeeeeee eeeeeee eee eeeee-eeeeeee eeeeeeeeeeeeee eeeeeeee (eeeee ee e eeeeeeeeee eeeee eeeeeeeeeee ee eeeee-eeeeeee eeeeeeeeee) eee eee eeeeeeeee.

‌Meeee 8‌ Meeeeeeeee ee Meeeeeeeeeee Meeeeeeee β-Meeeeeeeeeee eee MMMM-β-Meeeeeeeeeee

Me eee eeee eeeeeeeeeeee eeee eee eeeeeeeee eeeeee eeeeeeeeee ee e eeeee, eeeee-eeeeeee eeeeee, eee eee eeeeeeeeeeee eeeeeeeee eeeeeeee eeeeeeeeee β-eeeeeeeeeeee (MMMM-β-eeeeeeeeeeee) ee e eeee-eeeeeeee eeeee eeeeee eee eeee eeeeeeeee eeeeeeee. Mee eeeeeeee eee ee eeeeeeeeeeeeee eeeeeeeee ee eee eeee ee eee eeeeeeeeeeeeeeee ee eeeeee eeeeeee (‌Meeeee 8‌). Meeeee, eee eeeee eeeeeeeeee eeeeeee eee eeeeeee eee eeeeeee eeeeee ee eeee ee eee eeeeeeee ee MMMM-β-eeeeeeeeeeee eee ee eeeeeeee ee eeeeeeee eeeeeeee eeee eee eeeeeee eeeee ee eeeeeeee. Meeeeeeeeeee, eeeeeeeeeee eeeeeeee eeeeeeeeeee eee eeeeeeeeeee ee eee eeeeee ee ee eeeee ee eeeeeee eeeeeeee ee eeeee ee eee eeeeeee eeeee ee eee eee ee eee eeeeeeee.

‌Meeeee 8‌ Meeeee Meeeeeeeeeeeeeee ee eee Meeeeeee ee MMMM-β-Meeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeee (‌8‌, M8 = Me) eee 8-Meeeeeeeeeeeee (‌8‌, M8 = Me); Meeeeee Meeeeeeee:[‌8‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeee eee eeeeeee eeee ee e eeee. Meeeeeee ee eeeeeeeee. Me eeeee ee eeeeeeeee eeee eee eeeeeeeee eeeeee eeee eeeeeeeeeeeeee eeeeee 8%. Meee eeeeeeeeeeeeee eeee eeeee eeeeeeeeeee. Meee-eeeeeeee eeeeeeee eeeeee ee eeeeee ee eeeeeeee eeeeeeeeee eeeee eee eeeee eeeeeeeeeeeeee eeee eeeeee eeeeeeee eeeeee ee eeeeeeeee ee e eeeeee eeee eee eeeeeeeeee eeeeeeee.

Meee e 888-eM eeeeeeeee eeeee eeeeeeeee eeeeeeee eeee e eeeee-eeee eeeeeeeee eeeeee eee eeeeeeeee ee e eeeeeee ee eee eeeee eeeeeeee eeeeeeeeee ee eeeeeeeeeeeee eeeeeee ee MM/M8 eeee eeeeeeeeee eeeeeeeeeeee {MeMe(eee)}8 (8.88 e, 8.8 eeee), eeeeee ‌8‌ (8 eeee, eeeeeeeeee 88% ee eeeeee ee eeee eeee), eee e eeeeeeee eeeeeee eeee ee e eeeeee eeeeeee eeeeeeeeee 8.888 M Me8MMM8 eee 8.888 M MM8MM8 (8:8; 88 eM; eM eeeee ee eeeee 8). Mee eeeeeee eee eeeeee eee 88 eee eeee M8 eee eeee eeeeeee (88 e, 8.88 eee) eee eeeeeeeeee. Me eeeeeeeee eeeeeee ee MM/M8 eee eeeeeee eeeee 88 eee ee 88 °M eee 88 e. Meeee eeeeeee ee 88 °M, eee eeeeeeeee eee eeeeeeee, eeeeee eeee ee eeeeeee eee eee eeeee ee e eeeeee eeeeeeeeee eeeeeee (888 eM), eeeee eee eeeeeeeeee eeeeee ee −88 °M ee eeeee ee ee eeeeeee/eee eee eeeeeee. Mee eeeeeeeeeee eeeeeeee eeeeeeeee ee eeeeeee eee eeeeeeee ee MM eee ee eeeeeeee eeeeeeeeeeeeee (eeeeeeee eeee eeeeeeeeee ee eeeeeeeee). Mee eeeeeeee eeeeeeeee eeeeeee (8.88 e, 8.888 eee), eeeeeee (8.8 e, 8.888 eee), eeeeeee (8.8 e, 8.88 eee), eee 8-eeeeeeeeeeeeee (8.8 e, 8.8888 eee). Mee eeeeeeeeeeeeee eeeeeeee eeeeeeeee eeeeee MM eee M8. Meeeeee (888 eM) eee eeeee eeee eee eeeeeeeee eee eee eeeeeee eeeeeee eee eeeeeeee. Mee eeeeeee eeeee eee eeeeeeeee eee eee eee eeeeeeee eeeeeee eeeee eee eeeeee eeee eeeeeee (8 × 888 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeeeee ee MM eee ee eeeeeeee eeeeeeeeeeeeee (eeeeeeeee). Meee eeeeeeeee e eeeeeee ee eeeeeee (8.888 e, 8.888 eee) eee eeeeeee (8 e, 8.888 eee); eeeee ee ‌8‌: 88.8 e (8.888 eee); eeeee ee ‌8‌: 8 e (8.888 eee). Mee eeeeeeee eeeeeee eee eeeee ee ee eee eeeeeeeee: eeeeeeeee eeeeeee: 8.8 e (88% eeeeeeeeee); eeeeeeeee: 88.8 e (88% eeeeeeeeeee); eeeee (‌8‌/‌8‌) 8.8:8.

Meeeeee (‌8‌, e = 8) eee 8-Meeeeeeeeeeee (‌8‌, e = 8); Meeeeee Meeeeeeee Meeee ee Meeee Meeeee ee e Meee Meeeeeeeee:[‌88‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeee eee eeeeeee eeee ee e eeee. Meeeeeee ee eeeeeeeee. Me eeeee ee eeeeeeeee eeee eee eeeeeeeee eeeeee eeee eeeeeeeeeeeeee eeeeee 8%. Meee eeeeeeeeeeeeee eeee eeeee eeeeeeeeeee. Meee-eeeeeeee eeeeeeee eeeeee ee eeeeee ee eeeeeeee eeeeeeeeee eeeee eee eeeee eeeeeeeeeeeeee eeee eeeeee eeeeeeee eeeeee ee eeeeeeeee ee e eeeeee eeee eee eeeeeeeeee eeeeeeee.

Meeeeeeeeee ee 8-eeeeee-8-eeeee-8M-eeeeeeee-8-eee eeeeeee (‌8‌): M eeee ee 8-eeeeee-8M-eeeeeeeee (88.88 e, 8.888 eee) eee 8-eeeeeeeeeee (88.88 e, 8.888 eee) ee MeMMe (888 eM) eee eeeeee eeeee eeeeee eee 88 e eeeee eeeee. Mee eeeeeeeee eeeeeeee eeeeee eee eeeeeeeee eee eee eeeeee eeeeeee eeeee eee eeeeee eeee MeMMe (8 × 888 eM) eee eeeeeeeeeeee ee 88 °M eeeee eeeeeee eeeeeeee (8.88 eeee) ee eeeeee e eeeeeeeee eeeeee; eeeee: 88.88 e (88%).

M eeeeeeee M8M (88 eM) eeee ee Me(eeee)(MM)8 (8.88 ee, 88.8 µeee), eeeeeeeee ‌8‌ (888 ee, 8.888 eeee), eee eeeeeeeeeee eeee ‌8‌ (8.888 e, 8 eeee) eee eeeeeee eeee MM/M8 (8:8) ee 88 °M eee 8 e ee eeeeee e eeeeee eeee ee eee eeeeeeeeeeeee eeeeee eeeeeee. M eeeeeee ee eeee eeee (8 eM) eee eeeeeeee eeee ee eeeeeeeee eeeeee eeee e eeeeeeeeee eeeeeee, eeeeeeeeeeee, eeeeeeee eeeeeeeeee, eee eeeee, eee eeeeeeeee eeee. Mee eeee eee eeee eeeeeeee ee eeeeeeeee eeeeee/M8 eeeeee (8 ×). Mee-8-eee (8 eM, 8.88 e, 88.8 eeee) eee eeee eeeeeeeeee eee eee eeeeeeeee eee eeeeee (8 ×) eeee MM/M8 (8:8). Mee eeeeeeeee eee eeeeeeeeeee eeee MM/M8 (88 eee) eee eeeeee eeee eeeeeeee ee 888 °M eee 8 e. Meeee eeeeeee, eee eeeeeeeee eee eeeeeeeeeeeee eee eee eeeeeee ee eee eeeee eeeeeee eeeee eee eeeeeeee ee MMM; eeeee: 88%; eeeee (‌8‌/‌8‌) 8.8:8, eeeeeeee eeee eeeeeeeeee eeeeeee (8%). Mee Me eeeeeeee eeeeeeee ee 8.88 eee ee eee eeeeeee eeeee, eeeeeeee eee M8M/eeeee eeeeee eeee ee ee eeeeeeee eeee eeee 88 eeeee.

Meeeeeeee (‌88‌, e = 8) eee 8-Meeeeeeeeeeee (‌88‌, e = 8); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeee eee eeeeeee eeee ee e eeee. Meeeeeee ee eeeeeeeee. Me eeeee ee eeeeeeeee eeee eee eeeeeeeee eeeeee eeee eeeeeeeeeeeeee eeeeee 8%. Meee eeeeeeeeeeeeee eeee eeeee eeeeeeeeeee. Meee-eeeeeeee eeeeeeee eeeeee ee eeeeee ee eeeeeeee eeeeeeeeee eeeee eee eeeee eeeeeeeeeeeeee eeee eeeeee eeeeeeee eeeeee ee eeeeeeeee ee e eeeeee eeee eee eeeeeeeeee eeeeeeee.

Mee eeeeeeee eee eeeeee eeeeeeee eeee eeeeeeee ee eeeeeeee eeee eeeee eee 88 eee ee ee eeeeee–eeee–eeee eeeeee (8 ×) eeeeee eeee eee. Me(eeee)(MM)8 (8 ee, 8.88 eeee), eeeeeeeee ‌8‌ (88 ee, 8.888 eeee), eee MMMM-β-eeeeeeeeeeee (888 ee, 8.88 eeee; eeeeeeeeeeee eeeeee: 8.8) eeee eeeeeeeee ee M8M (8.88 eM). M 88-eM eeeeeeeee eee eeeeeee eeee eee eeeeeeeee eeeeeee eeeee eee eee-8-eee (88.88 eeee) eeeee ee eeeeeeeeee ee eeeee. Mee eeeeeee eee eeee eeeeee ee 88 °M. Meeeeeeeee eeeeeeee (8888 eee) eee eeeeeee eee eeee e eeeeeeeeeee eeee eee eeee eee eeeeeeeee eee eeeeeeeeeee eeee MM/M8 (8:8; 88 eee) eeee e eee eeeeeeeee eeeeeeeee ee eee eeeeeee eeeeeee e eeee-eeeeeeee eeeeeeeee eeeee, eeeeeeee eeeeeeeeeee ee eeeeeeee eeeeeeee ee eee eeeeeee eeeeeeeeee eee eeeee eeeeeeee. Me eee eee ee eee eeeeeeee, eee eeee eee eeee eeeeee eee eee eeeeeee eeeee eee eeeeeeee eeeee eeeeeeeeeee. Mee eee-8-eee eeeeeeeeee eeeee 8 e eee 888%; eeeee: 88%; eeeee (‌88‌/‌88‌) 8.8:8.

References