Synthesis, complexation behavior and application of a new diphosphite ligand in rhodium-catalyzed hydroformylation

Synthesis of Adipic Aldehyde by n-Selective Hydroformylation of 4-Pentenal

“…The molecular structure of L10 is shown in Figure . Similar rearrangements of bisphosphite ligands were reported previously and may actually represent a simple approach toward asymmetric ligands. , …”

“…Similar rearrangements of bisphosphite ligands were reported previously and may actually represent a simple approach toward asymmetric ligands. 27,28 The ligand screening for the hydroformylation of 4-pentenal was done at 60 bar syngas pressure (CO/H 2 1:1), 80 °C, and 2 h reaction time in a Chemspeed high-throughput robot system (see Experimental Section for details). The results are shown in Table 1.…”

Applied Hydroformylation

“…100 Recently, it was demonstrated that this side-reaction, which probably occurs through the formation of a bicyclic hydrophosphorane, can be advantageously used for the construction of a nonsymmetric diphosphite (Scheme 7). 101 A similar transesterification process was observed in the reaction of biphenolphosphorochloridite with o-phthalic acid, where only the corresponding pyrophosphite was produced (Scheme 8). 102 Synthesis of the targeted diphosphite could be achieved only with m-phthalic acid.…”

“…Attention should be given to the second esterification step, because transesterification at the stage of the monoester may occur, which lowers the yield of the desired ligand . Recently, it was demonstrated that this side-reaction, which probably occurs through the formation of a bicyclic hydrophosphorane, can be advantageously used for the construction of a nonsymmetric diphosphite (Scheme ) …”

Rhodium‐Catalyzed Asymmetric Hydrohydrazonemethylation of Styrenes: Access to Chiral Hydrazones, Hydrazides, Hydrazines and Amines

“…1k gave the corresponding product 7k in 88% yield and 87% ee, whereas the electron-rich and bulky mesitylene derivative 1o did not show any reactivity, although the hydroformylation of 1o with other catalyst systems was reported before. [23] Next, a method for the cleavage of the acetyl group in 7a was developed. Whereas hydrolysis with aqueous HCl led to product decomposition, the acid catalyzed methanolysis with hydrogen chloride in MeOH/Et 2 O under water free conditions led to the selective formation of the monohydrochloride of (R)-(2phenylpropyl)hydrazine ( 8) and methyl acetate as volatile by-product.…”