Catalyse d'hydrogenation en phase homogene des aldehydes α-β insatures. Application a la synthese asymetrique du citronellal

Dang, T. P.; Aviron-Violet, P.; Colleuille, Y.; Varagnat, J.

doi:10.1016/0304-5102(82)80063-1

Cited by 46 publications

(4 citation statements)

References 7 publications

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“…64 This is an unusual, selective hydrogenation of the double bond in conjugation with the aldehyde functionality that does not touch the other alkene or the aldehyde functionality. Following literature leads, 65,66 the authors examined the use of CO containing rhodium precursors in the asymmetric hydrogenation of neral. A detour through an extensive ligand screen in high throughput mode finally brought the authors back to the original Chapuis ligand, Chiraphos (28).…”

Section: L-mentholmentioning

confidence: 99%

Asymmetric homogeneous hydrogenations at scale

Ager¹,

2012

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Asymmetric hydrogenations are increasingly being used to introduce stereogenic centres into products used in the life sciences industries. There are a number of potential pitfalls when moving from a laboratory reaction to a manufacturing process, not least of which is safety. Time-to-market pressure leads to short development times, which in the past could be a large barrier for the implementation of catalytic steps; now there are new ways to minimise this problem. The potential problems associated with impurities and other methods that can shut down the hydrogenation reactions are highlighted in this critical review (353 references).

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Section: L-mentholmentioning

confidence: 99%

Asymmetric homogeneous hydrogenations at scale

Ager¹,

2012

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“…Then, reduction of ( S )-citronellal (( S )- 11 ) gave ( S )-citronellol (( S )- 37 ) . Recently, rhodium-catalyzed hydrogenation of neral (( Z )- 10 ; E / Z 0.9/99.1) was also reported to give ( S )-citronellal (( S )- 11 ) in high enantioselectivity (90% ee) with the chiral diphosphine ( S , S )-Chiraphos . On the other hand, the hydroxyl-directed CC bond hydrogenation of nerol or geraniol (( E )- 40 ) catalyzed by ruthenium complex 4 gave access to ( S )-citronellol (( S )- 37 ) in high enantioselectivity (98% ee) .…”

Section: Ingredients Responsible For Floral Odormentioning

confidence: 99%

Hydrogenation Processes in the Synthesis of Perfumery Ingredients

Saudan

2007

Acc. Chem. Res.

224

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Homogeneous catalytic hydrogenation has played an important role in the development of modern organic synthesis. Indeed, the discovery of highly regio- and stereoselective catalysts for C=C and C=O bonds reductions has allowed the efficient synthesis of optically active compounds. As the fragrance industry has turned to synthetic ingredients to fulfill the need for novel, cost-effective, and environment-friendly products, the use of catalytic processes are more and more in demand. In this Account, we thus highlight the application of catalytic hydrogenation in the synthesis of fragrance ingredients.

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“…Indeed, of all eight stereoisomers, with respect to the Rh center, those whose allylamine is facing the bulky di(tertbutyl)phosphino moiety, are much higher in energy than B. Similarly, the structures where the RhÀH bond is syn-periplanar to the pseudoaxial PÀPh bond are also higher in energy than B or C. This latter intermediate, 1.2 kcal/mol higher in energy than B 16 ), is an epimeric cyclometalated allylamine at C(1), generating the (E)-enamine of opposite topicity. It is noteworthy that, in contrast to the seven-membered ring chelate of binap, the pseudoaxial/equatorial RhÀPh bonds are pointing in slightly different directions with respect to those of the distorted six-membered ring of the (R,S)-13 complex.…”

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confidence: 97%

“…We are particularly indebted to Prof. Salzer for providing us with these unreported non-commercial diphosphino ligands. 16 ) Due to its simplification, this model is only qualitative, allowing a better evaluation of the acceptable coordination possibilities.…”

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confidence: 99%

Synthesis of Citronellal by RhI-Catalysed Asymmetric Isomerization ofN,N-Diethyl-Substituted Geranyl- and Nerylamines or Geraniol and Nerol in the Presence of Chiral Diphosphino Ligands, under Homogeneous and Supported Conditions

Chapuis¹,

Barthe²,

Laumer³

2001

HCA

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For the asymmetric isomerization of geranyl-or neryldiethylamine ((E)-or (Z)-1, resp.) and allyl alcohols geraniol or nerol ((E)-or (Z)-2, resp.) to citronellal (4) in the presence of a [Rh I (ligand)cycloocta-1,5-diene)] catalyst, the atropic ligands 5 ± 11 are compared under homogeneous and polymer-supported conditions with the non-C 2 -symmetrical diphosphino ferrocene ligands 12 ± 16. The t Bu-josiphos ligand 13 or daniphos ligand 19, available in both antipodal series, already catalyse the reaction of (E)-1 at 208 (97% e.e.) and favourably compare with the binap ligand 5 (see Table 1). Silica-gel-or polymer-supported diphosphino ligands usually afford similar selectivity as compared to the corresponding ligands applied under homogeneous conditions, but are generally less reactive. In this context, a polymer-supported ligand of interest is the polymer-anchored binap (R)-6, in terms of reactivity, selectivity, and recoverability, with a turnover of more than 14400.

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Catalyse d'hydrogenation en phase homogene des aldehydes α-β insatures. Application a la synthese asymetrique du citronellal

Cited by 46 publications

References 7 publications

Asymmetric homogeneous hydrogenations at scale

Asymmetric homogeneous hydrogenations at scale

Hydrogenation Processes in the Synthesis of Perfumery Ingredients

Synthesis of Citronellal by RhI-Catalysed Asymmetric Isomerization ofN,N-Diethyl-Substituted Geranyl- and Nerylamines or Geraniol and Nerol in the Presence of Chiral Diphosphino Ligands, under Homogeneous and Supported Conditions

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