Hydroformylation of olefins with formaldehyde in the presence of RhHCO(PPh3)3

Reactions of alkenes and alkynes with formaldehyde catalyzed by rhodium systems containing phosphine ligands

“…Regioselectivities towards the corresponding linear aldehyde were from moderate to high, being the most selective system Rh/2 dppe (l/b = 30). For comparison, under the same reaction conditions, the complex RhH(CO)(PPh 3 ) 3 displayed a good activity (36 TON in 4h) with high regioselectivity toward the linear aldehyde (l/b = 21), results which are concordant with those reported by Seok et al [11]. On the other hand, these systems were also active for the hydroformylation of styrene with formaldehyde (Eq.…”

“…In fact, for the hydroformylation of simple alkenes (1-hexene and styrene), the order of catalytic activity is Rh/2dppe > Rh/dppe > Rh/triphos > Rh/nPPh 3 , whereas for the hydroformylation of allyl alcohol (an alkene with oxygen atom in b position), the order is Rh/2dppe > Rh/ nPPh 3 > Rh/dppe > Rh/triphos. The higher activity of the Rh/ nPPh 3 systems for the hydroformylation of allyl alcohol compared with simple alkenes may be explained by the coordination of the OH group of the substrate to the metal center, which should hinder the decarbonylation of the formyl group; the coordination of OH group of the substrate to the metal center has been reported by Seok et al [11] for the hydroformylation of allyl alcohol and acrolein catalyzed by RhH(CO)(PPh 3 ) 3 . Although the hydroformylation of alkenes with formaldehyde catalyzed by Rh/2dppe proceeds via hydroacylation mechanism [24], the reaction catalyzed by Rh/nPPh 3 and Rh/1dppe systems probably proceeds through a classic mechanisms in view of experimental evidences obtained in the coordination chemistry reported in the present work (vide infra).…”

“…[6] in 1982. In the following three decades, the hydroformylation of unsaturated substrates with formaldehyde has been reported intermittently [7][8][9][10][11] and only recently this area has attracted significant interest, as emphasized by Franke et al [12] in a review on the hydroformylation reaction and its applications. In fact, some of us reported the potential of rhodium catalysts containing triphenylphosphine (PPh 3 ), diphosphines [Ph 2 P(CH 2 ) n PPh 2 ; n = 2, 3 and 4] and 1,1,1-tris(diphenylphosphino)ethane (triphos) in the hydroformylation with formaldehyde of 1-hexene (Eq.…”

Carbonylations of Alkenes with CO Surrogates

“…Almost 20 years later, Seoks group [29] used [RhHCO-(PPh 3 ) 3 ] in the presence of excess amount PPh 3 (5 equiv) to catalyze the reaction of alkenes with paraformaldehyde. The authors found that allyl alcohol and methyl acrylate, which both have oxygen at the b-position to the double bond, showed higher reactivity and regioselectivity to give the linear aldehyde than olefins without oxygen atoms such as propylene and hexene.…”

Carbonylierungen von Alkenen mit CO‐Alternativen

“…Hier wurden auch geringe Mengen an Hexanolen durch die Hydrierung des Aldehyds gebildet (Schema 9).Ungefähr 20 Jahre später verwendete die Seok-Gruppe[29] [RhHCO(PPh 3 ) 3 ] als Katalysator in Gegenwart eines Überschusses an PPh 3 (5 ¾quiv.) Bemerkenswerterweise wurde der einfachste Aldehyd, Formaldehyd, viel weniger in Carbonylierungen von Alkenen untersucht.…”