Tandem Hydroformylation–Hydrogenation of 1‐Decene Catalyzed by Rh‐Bidentate Bis(trialkylphosphine)s

Abstract

A series of 2,2'-bis[(dialkylphosphino)methyl]biphenyls (alkyl-BISBIs) were synthesized and applied to the tandem hydroformylation-hydrogenation of 1-decene. The alkyl-BISBI ligands with "small" primary alkyl groups such as methyl or n-hexyl groups on the phosphorus atoms provided 1-alkanols selectively, whereas those with larger alkyl groups such as isopropyl or neopentyl groups showed much lower conversion from alkanals to alkanols. Observation of rhodium complexes of the BISBI-type ligands under H(2)/CO atmosphere revealed that the presence of a stable [RhH(CO)(2)(ligand)] species seems to be less favorable for the second step, the hydrogenation of aldehydes.

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

“…[7,11] This approachh as been utilised in the Shell-process since 1960 in which phosphine-modified cobalt catalysts are used in the production of alcohols owing to their strong hydrogenation activity.H owever,t he reactionc onditions are harsh and high catalystl oadings are neededt oe nsure high yields. For many years, this tandem reaction has been intensively studied, using differentt ransition metal catalysts ystems based on Co, Ru [12][13][14][15] and Rh [16][17][18][19][20][21] with variousl igands as well as bicatalytic reactions. [22][23][24][25] Challenges still remain;i ncreasing reaction selectivity by reducing the amount of by-products such as alkanesa nd aldol condensation products is of particular interest.…”

Organic Synthesis: Mitsui Chemicals Catalysis Award to J. F. Hartwig and K. Nozaki / Early Career Awards for S. Matsunaga and Y. Nakao

“…Her research interests include homogeneously catalyzed polymer synthesis and organic synthesis. She recently reported in Angewandte Chemie on the synthesis, structure, and reactivity of boryl copper and boryl zinc compounds 1a and in Chemistry—an Asian Journal on a tandem hydroformylation–hydrogenation of 1‐decene with rhodium complexes of bis(trialkylphosphines) 1b …”

Organische Chemie: J. M. J. Fréchet ausgezeichnet / Katalyse: K. Nozaki geehrt / Metallorganische Chemie: Preis für P. Braunstein

“…Darüber hinaus entwickelt sie molekulare Katalysatoren für effiziente Reaktionen in der atomökonomischen und nachhaltigen Synthese von Wirkstoffen und neuen Materialien. In Chemistry—An Asian Journal berichtete sie kürzlich über die rhodiumkatalysierte Sequenz aus Hydroformylierung und Hydrierung von 1‐Decen2a und in der Angewandten Chemie über die 1,4‐Silaborierung eines α,β‐ungesättigten Ketons unter Bildung eines γ‐Siloxyallylborans 2b …”