Rhodium catalyzed hydroformylation of monoterpenes containing a sterically encumbered trisubstituted endocyclic double bond under mild conditions

Silva, José G. da; Barros, Humberto J.V.; Balanta, Angelica; Bolaños, Alberto; Novoa, Maria L.; Reyes, Marisela; Contreras, Ricardo R.; Bayón, J. Carles; Gusevskaya, Elena V.; Santos, Eduardo N. dos

doi:10.1016/j.apcata.2007.04.014

Cited by 28 publications

(13 citation statements)

References 19 publications

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“…Limonene aldehyde has a citrus odor and is used in soaps and lotions. Spirambrene® is manufactured by Givaudan and Vigon by hydroformylation of 2-carene [35,36]. Tollens reaction of the resulting aldehyde gives a diol which is converted to the acetal with acetone.…”

Section: Fragrancesmentioning

confidence: 99%

Applications of Rhodium-Catalyzed Hydroformylation in the Pharmaceutical, Agrochemical, and Fragrance Industries

Whiteker¹,

Cobley

2012

Organometallics as Catalysts in the Fine Chemical Industry

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This review summarizes the known commercial applications of rhodiumcatalyzed olefin hydroformylation to fine chemical synthesis. Two manufacturing processes for Vitamin A utilize hydroformylation. Additional, recent examples of hydroformylation on multikilogram scale for synthesis of pharmaceutical building blocks have also been reported. Hydroformylation appears to be widely used in the fragrance industry, where aldehydes are ubiquitous. Numerous fragrance ingredients are commercially prepared by hydroformylation. There are no reports of agrochemical manufacturing processes which employ hydroformylation. In addition to commercial applications, examples of pharmaceutical, fragrance, and agrochemical products which have been prepared on small scale using hydroformylation are given. Hydroformylation appears to be well suited to fine chemical synthesis, and applications should increase as process chemists become more aware of its potential.

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Section: Fragrancesmentioning

confidence: 99%

Applications of Rhodium-Catalyzed Hydroformylation in the Pharmaceutical, Agrochemical, and Fragrance Industries

Whiteker¹,

Cobley

2012

Organometallics as Catalysts in the Fine Chemical Industry

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“…Terpenes are an important biomass‐based renewable feedstock for the flavor and fragrance industries 17–19. For several years, we have been interested in the hydroformylation of terpenes and have directed our efforts to combine the hydroformylation step with other reactions in tandem processes 20–24…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Fragrance Compounds from Biorenewables: Tandem Hydroformylation–Acetalization of Bicyclic Monoterpenes

et al. 2013

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The Rhodium‐catalyzed tandem hydroformylation–acetalization of the terpenes 3‐carene, 2‐carene, α‐pinene, and β‐pinene was studied in ethanol solutions in the presence of PPh3 or tris(O‐tert‐butylphenyl)phosphate, P(O‐o‐tBuPh)3, ligands. All these terpenes are constituents of turpentine oils obtained commercially from coniferous trees. β‐Pinene gave the corresponding aldehyde and acetal in excellent combined yields in both systems. 3‐Carene, 2‐carene, and α‐pinene, which contain sterically encumbered endocyclic double bonds, showed an extremely low reactivity with PPh3. The use of P(O‐o‐tBuPh)3 not only accelerated the hydroformylation of all four substrates remarkably but also increased the acetalization activity of the catalyst. In the Rh/P(O‐o‐tBuPh)3 system, various fragrance acetals and aldehydes were obtained from these renewable substrates in nearly quantitative combined yields. The process was performed under mild conditions, in environmentally friendly ethanol as a solvent, and in the absence of acid cocatalysts.

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“…On the other hand, the stronger π-acid properties of the phosphite, in relation to those of phosphanes, weaken the Rh-CO bonds, allowing a fast substitution of the carbonyl ligand by the alkene, followed by the alkene insertion into the Rh-H bond, in what is assumed to be the rate-determining step of a hydroformylation of an encumbered alkene in the presence of the Rh/P(O-o-tBuC 6 H 4 ) 3 catalyst. [15] This catalyst is commercially used in hydroformylation of 3-methylbut-3-en-1-ol, [16] while its performance in the hydroformylation of sterically hindered alkenes such as cyclic ethers, [17] glucal derivatives, [18] fatty acids, [19] terpenes, [20] and steroids [21] has also been reported.…”

Section: Introductionmentioning

confidence: 99%

New Aldehydes by Catalytic Diene Cycloisomerisations

et al. 2008

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Rhodium catalyzed hydroformylation of monoterpenes containing a sterically encumbered trisubstituted endocyclic double bond under mild conditions

Cited by 28 publications

References 19 publications

Applications of Rhodium-Catalyzed Hydroformylation in the Pharmaceutical, Agrochemical, and Fragrance Industries

Applications of Rhodium-Catalyzed Hydroformylation in the Pharmaceutical, Agrochemical, and Fragrance Industries

Synthesis of Fragrance Compounds from Biorenewables: Tandem Hydroformylation–Acetalization of Bicyclic Monoterpenes

New Aldehydes by Catalytic Diene Cycloisomerisations

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