Catalytic hydroformylation of (1S,5S)-(−)- and (1R,5R)-(+)-β-pinene: stereoselective synthesis and spectroscopic characterization of (1S,2R,5S)-, (1S,2S,5S)-, (1R,2R,5R)- and (1R,2S,5R)-10-formylpinane

Azzaroni, Fabrizio; Biscarini, P.; Bordoni, Silvia; Longoni, Giuliano; Venturini, Emanuela

doi:10.1016/0022-328x(95)05778-n

Cited by 32 publications

(12 citation statements)

References 22 publications

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“…Although the hydroformylation of more abundant monoterpenes, such as limonene, ␤-pinene, myrcene and camphene, was quite extensively studied [11][12][13][14][15][16][17][18][19][20], only few reports appeared on the hydroformylation of linalool [11,[21][22][23] and ␤-citronellene (dihydromyrcene) [11,24,25]. Linalool, a monoterpenoid allylic alcohol with a pleasant lily odor, is a key building block for the synthesis of various vitamins and fragrances, such as vitamin A, vitamin E, citral and citronellol [3,4].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of fragrance compounds from acyclic monoterpenes: Rhodium catalyzed hydroformylation and tandem hydroformylation/acetalization of linalool and β-citronellene

Vieira

Santos

Gusevskaya

2013

Applied Catalysis A: General

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Rhodium-catalyzed hydroformylation of acyclic monoterpenic compounds, i.e., linalool and ␤citronellene, was studied in toluene and ethanol solutions in the presence of PPh 3 or P(O-o-t BuPh) 3 ligands. Although both substrates have a monosubstituted terminal double bond, they show different behavior under the hydroformylation conditions. In toluene, linalool gave almost quantitatively a cyclic hemiacetal; whereas the hydroformylation of ␤-citronellene resulted in two isomeric aldehydes also in a nearly quantitative combined yield. The reactions occurred approximately two times faster in ethanol than in toluene giving the corresponding acetals even in the absence of additional acid co-catalysts. In the absence of phosphorous ligands, linalool (differently from ␤-citronellene) was very resistant to hydroformylation probably due to the binding with rhodium through both the double bond and the hydroxyl group to form stable chelates. The P(O-o-t BuPh) 3 ligand exerted a remarkable effect on the reactivity of both substrates accelerating the reactions by 5-20 times as compared to the system with PPh 3. Several fragrance compounds were obtained in high yields through a simple one-pot procedure starting from the substrates easily available from natural bio-renewable resources.

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Section: Introductionmentioning

confidence: 99%

Synthesis of fragrance compounds from acyclic monoterpenes: Rhodium catalyzed hydroformylation and tandem hydroformylation/acetalization of linalool and β-citronellene

Vieira

Santos

Gusevskaya

2013

Applied Catalysis A: General

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“…trans ‐10‐Formylpinane (4 b trans ) (shorter GC retention time): MS (70 eV, EI): m / z (%): 166 (0.7) [ M + ], 133 (17), 123 (33), 122 (57), 109 (18), 107 (46), 105 (22), 95 (26), 93 (30), 91 (23), 83 (34), 82 (42), 81 (58), 80 (22), 79 (97), 78 (22), 77 (19), 69 (64), 68 (19), 67 (70), 66 (17), 56 (20), 55 (100), 53 (21), 43 (26), 41 (87). Compounds described by Azzaroni et al 25. and Sirol and Kalck 28…”

Section: Methodsmentioning

confidence: 98%

“…The hydroformylation of β‐pinene, an alkene that has a disubstituted terminal double bond, can be achieved easily in Rh‐based systems 25–30. However, the hydroformylation of α‐pinene,24, 28–33 3‐carene,31, 24 and 2‐carene24 is more troublesome because of the steric crowdedness of their endocyclic trisubstituted double bonds.…”

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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“…The balance between the competitive reactions during the hydroformylation of a-pinene seems to be affected by the reaction conditions such as the P/Rh ratio and pressure (cf. Table 4, entries [19][20][21]. The low diastereoselectivity of the hydroformylation of b-pinene reflects the fact that the discrimination between the two diastereotopic faces in bpinene is much more difficult than for a-pinene and carenes.…”

Section: Hydroformylation Of A-pinenementioning

confidence: 99%

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

Silva

Barros

Balanta

et al. 2007

Applied Catalysis A: General

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Catalytic hydroformylation of (1S,5S)-(−)- and (1R,5R)-(+)-β-pinene: stereoselective synthesis and spectroscopic characterization of (1S,2R,5S)-, (1S,2S,5S)-, (1R,2R,5R)- and (1R,2S,5R)-10-formylpinane

Cited by 32 publications

References 22 publications

Synthesis of fragrance compounds from acyclic monoterpenes: Rhodium catalyzed hydroformylation and tandem hydroformylation/acetalization of linalool and β-citronellene

Synthesis of fragrance compounds from acyclic monoterpenes: Rhodium catalyzed hydroformylation and tandem hydroformylation/acetalization of linalool and β-citronellene

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

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

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