Rhodium-catalyzed hydroaminomethylation of cyclopentadiene

Abstract

A one-step rhodium catalyzed direct route from cyclopentadiene (Cpd) to saturated C 6 -amines is presented via hydroaminomethylation (HAM). The homogeneous catalyst of Rh(II) octanoate dimer without additional phosphorus ligands was established giving a 77% yield of the monoamine species of Cpd with pyrrolidine within 4 hours. The unwanted reaction of Cpd, the dimerization to dicyclopentadiene (Dcpd), could be suppressed by careful adjustment of the CO : H 2 ratio in the synthesis gas and the choice of solvent, both giving the possibility to steer the reaction to selectively produce amines of either Cpd or Dcpd. Furthermore, other investigated cyclic and non-cyclic aliphatic amine substrates showed excellent selectivity up to 100% for the formation of the HAM-products. CH 3 ); 2.80 (m, 2H, 2CH); 2.21-2.24 (m, 1H, CH); 2.16 (d, 3 J ( 1 H-1 H) ¼ 8 Hz, 2H, CH 2 ), 1.96-2.00 (m, 1H, CH); 1.88-1.92 (m, 2H, 2CH); 1.80 (m, 2H, 2CH); 1.65-1.71 (m, 4H, 2CH 2 ); 1.78-1.82 (m, 2H, 2CH) 1.43-1.53 (m, 4H, 2CH 2 ); 1.10-1.15 (m, 2H, 2CH). 13 C( 1 H) (125.77 MHz, CDCl 3 , TMS) d 13 C [ppm]: 175.95 (s, 1C); 60668 | RSC Adv., 2015, 5, 60667-60673 This journal is Scheme 1 Product range in the hydroaminomethylation of Cpd 1 with pyrrolidine.This journal is

Tertiary Amines as Ligands in a Four‐Step Tandem Reaction of Hydroformylation and Hydrogenation: An Alternative Route to Industrial Diol Monomers

“…Starting conditions for our investigation of the hydroformylation and hydrogenation were chosen based on the hydroaminomethylation of cyclopentadiene recently published by our group. [43] Dicyclopentadiene( dcpd 1)w as selected as model substratef or non-conjugated dienes because of its high industrial importance.G iven that dcpd 1 has two differentially reactive doubleb ounds,h ydroformylation is most likely to occur initially on norbornenyl moiety to yield TCD-monoaldehyde 2 (Scheme2). Subsequenth ydroformylation either forms dialdehyde 4 or TCD-monoaldehyde 2.T he latter is hydrogenated to TCD-monool 3.…”

Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

“…Transition metal catalyzed tandem catalyses often involve hydroformylation as the initial reaction step to form reactive aldehydes [14], which constitutes a well investigated reaction that is also the subject ongoing research [15][16][17]. Hydroformylation is an important part of the hydroaminomethylation, which is a three step autotandem catalysis catalyzed by a single catalyst [16,[18][19][20][21][22][23][24]. Past investigations have applied different renewables [25][26][27][28][29][30] in the hydroaminomethylation reaction to increase the sustainability of the overall reaction sequence.…”

Renewable Surfactants through the Hydroaminomethylation of Terpenes

“…None of the hydroaminomethylations mentioned above consist of a hydroformylation of conjugated 1,3‐dienes but rather isolated terminal double bonds. The only reported hydroaminomethylations of conjugated 1,3‐dienes are isoprene and cyclopentadiene . Both reactions suffer from low regioselectivity of the hydroformylation, on the one hand, and low catalytic activity of rhodium if applied to 1,3‐dienes, on the other .…”