137625-67-3Relevant academic research and scientific papers
Dauben-Michno oxidative transposition of allylic cyanohydrins - Enantiomeric switch of (-)-carvone to (+)-carvone
Hudlicky, Jason R.,Werner, Lukas,Semak, Vladislav,Simionescu, Razvan,Hudlicky, Tomas
, p. 535 - 543 (2011/10/03)
Allylic cyanohydrins were subjected to Dauben-Michno oxidation at low temperatures to provide β-cyanoenones in good to excellent yields. The potential of this oxidative transposition as a means of an enantiomeric switch of enones containing a latent plane of symmetry was tested by conversion of (-)-carvone to its enantiomer.
Synthesis of (R)-(-)-carvone derivatives
De Sousa, Damia?o P.,Raphael, Ellen,Brocksom, Timothy J.
scheme or table, p. 1381 - 1383 (2011/01/10)
(R)-(-)-Carvone, the main constituent of spearmint oil, has several synthetic applications and is used in cosmetics, food, and pharmaceutical preparations. In a recent study we demonstrated that (R)-(-)-carvone shows significant analgesic activity. In the
Synthesis and analgesic-like effect of (6R, 4S)-p-Mentha-1,8-dien-6- ylmethylene-p-toluenesulfonamide
Sousa, Damiao P.,Nobrega, Franklin F. F.,Almeida, Reinaldo N.,Brocksom, Timothy J.
scheme or table, p. 351 - 355 (2009/06/17)
The synthesis of a monoterpene-based para-toluenesulfonamide is reported starting from naturally occurring (R)- (-)-carvone (1), by 1,2-addition of HCN followed by reduction with lithium aluminum hydride to afford the amino alcohols 3a and 3b. Tosylation
A recyclable chiral auxiliary for the asymmetric syntheses of α-aminonitriles and α-aminophosphinic derivatives
Rossi, Jean-Christophe,Marull, Marc,Larcher, Nicolas,Taillades, Jacques,Pascal, Robert,van der Lee, Arie,Gerbier, Phillipe
, p. 876 - 883 (2008/09/21)
Optically active α-aminonitriles and α-aminophosphinic derivatives have been prepared in high yield and high ee using an easy route by extending our previously developed method involving the following sequence: (i) stereoselective Strecker condensation of
Regioselective hydration and deprotection of chiral, dissymmetric iminodinitriles in the scope of an asymmetric strecker strategy
Rossi, Jean-Christophe,Marull, Marc,Boiteau, Laurent,Taillades, Jacques
, p. 662 - 668 (2007/10/03)
The controlled, selective decomposition of dissymmetric iminodinitriles (DIDN) of formula RCH(CN)-NH-C(CN)R′R″ (considered as N-protected alpha-aminonitriles), is a critical issue for an original asymmetric Strecker strategy previously outlined by us for the enantioselective synthesis of amino acids. This strategy, derived from Harada's work, involves a double sequence of (i) stereoselective Strecker condensation of a chiral ketone R′R″CO with NH3 and HCN, followed by (ii) stereoselective Strecker condensation with an aldehyde RCHO and HCN, then (iii) regioselective retro-Strecker decomposition of the DIDN intermediate to release the target alpha-aminonitrile. In addition to the use of quite simple, cheap cyclic ketones (e.g. carvone derivatives) as chiral auxiliaries, another great advantage of this strategy is that step (iii) enables the recovery of the chiral ketone and hence its reuse. While our previous investigations on step (iii) under various conditions, either preceded or followed by the hydration of the secondary nitrile group RH(CN)- into an amide, had shown insufficient selectivity, we succeeded in the regioselective hydration of the secondary nitrile of DIDN without significant racemisation, by using a large excess of hydrogen peroxide in methanolic/aqueous ammonia (pH 12.5) at low temperature. The resulting imino nitrile/amide compound was then classically decomposed in acidic medium through a retro-Strecker reaction, affording the chiral alpha-amino amide. Alternately, the regioselective retro-Strecker decomposition of the tertiary moiety of the DIDN was achieved by reaction with silver cation in aqueous nitric acid, also without significant racemisation, thus establishing an original, enantioselective synthesis of alpha-aminonitriles. In both reactions, the chiral ketonic auxiliary resulting from DIDN decomposition was recovered in good yields. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Hydrocyanation of some α,β-unsaturated ketones, and the synthesis of some unusual isoxazoles
Cocker, Wesley,Grayson, David H.,Shannon, Patrick V. R.
, p. 1153 - 1162 (2007/10/02)
β-Cyano-α-methylcycloalkanones are regiospecifically nitrosated at the α-position by pentyl nitrite in methanolic sodium methoxide to give fused isoxazolo-lactams via a pathway probably involving sequential cycloalkanone cleavage, isoxazole formation and lactamisation.The chamistry of some new compounds derived from the hydrocyanation products of (-)-carvone is described.
Auxiliary chiral ketones in the asymmetric synthesis of α-amino acids by Strecker reaction
Bousquet, C.,Tadros, Z.,Tonnel, J.,Mion, J.,Taillades, J.
, p. 513 - 520 (2007/10/02)
The asymmetric synthesis of α-aminoamides 1 R1CH(CONH2)NH2 1 = Ph-CH2, 1b: R1 = Pri, 1c: R1 = Ph> that leads to the corresponding α-amino acids is achieved by a classical Strecker reaction 1CHO, HCN, NH3> using an auxiliary chiral ketone (R2R'2CO) as a catalyst.In the presence of an aqueous solution of HCN and NH3, the (-)-5R-(methylethenyl)-3R-cyano-2R-methylcyclohexanone 2(-) leads to the 5R-(methylethenyl)-3R-cyano-2R-methyl-1R-cyano-cyclohexylamine 3 with 80percent stereoselectivity.Following condensation with R1CHO, this α-aminonitrile R2R'2C(CN)NH2 3 yields the corresponding iminonitrile which undergoes a second asymmetric addition of HCN yielding an asymmetric α-aminodinitrile 4 R2R'2C(CN)-NH-CHR1(CN) with stereoselectivity that varies betweeen 62percent (R1 = Ph) and 79percent (R1 = Ph-CH2).The α-aminodinitrile obtained as the major product undergoes regioselective hydration of the secondary aminonitrile moiety followed by the decomposition ("retro-Strecker") of the tertiary aminonitrile moiety yielding an optically active α-aminoamide (eg 78percent optical purity for 1a) and the auxiliary chiral ketone 2 and ketonic derivatives.Keywords - α-aminonitrile / α-amino acid / asymmetric synthesis
Influence of a Hydroalcoholic Solvent on the Enantioselectivity of α-Amino nitrile Hydration Catalysed by Chiral Ketones
Lagriffoul, Pierre-Henri,Tadros, Ziad,Taillades, Jacques,Commeyras, Auguste
, p. 1279 - 1285 (2007/10/02)
The enantioselective hydration of α-aminonitriles 1, RCH(CN)NH2 i; 1c: R = Ph> has been achieved in an alkaline hydroalcoholic medium in the presence of chiral ketonic catalysts.Of the different ketones used, (-)-(5R,3R,2R)-5-(methylethenyl)-3-cyano-2-methylcyclohexanone (8) gives rise to significant enantioselectivity D/kL = 2.1; T = 10 deg C; solvent, water-propan-2-ol (45:55,v/v)>.Although the structure of the catalyst could probably be improved, we show in this paper that the efficiency and especiallythe enantioselectivity of the catalyst are not only under steric control but also depend on the nature and composition of the hydroalcoholic solvent.Thus, for the three aminonitriles studied in the presence of the catalyst 8, the increase in percentage of propan-2-ol favours the hydration of the D α-aminonitrile as shown for the hydration of 1c for which the ratio kD/kL increases threefold when the percentage of propan-2-ol increases from 10 to 95percent.
Hydratation enantioselective d'α-aminonitriles en presence de catalyseurs cetoniques chiraux supportes
Taillades, J,Garrel, L.,Lagriffoul, P. H.,Commeyras, A.
, p. 191 - 198 (2007/10/02)
Enantioselective hydration of α-aminonitriles with chiral ketonic immobilized catalyst.In a previous publication, we showed that the hydration of α-aminonitriles under basic aqueous conditions was efficiently catalyzed by a poly(N-acryloylpiperidin-4-one) crosslinked with 20percent N,N'-bisacryloylpiperazine.In this paper, we show that lowering the degree of crosslinking and diluting piperidone sites inside the polymeric matrix by copolymerisation with an inactive comonomer (N-acryloylmrpholine), decrease catalyst degradation and improve average reactivity ofcatalytic sites.The best results were obtained with a 5percent crosslinked resin containing 15percent piperidin-4-one sites.With the same proportions, we prepared a polymer-supported chiral ketone 14 which catalyzes the enantioselective hydration of α-aminobenzylacetonitrile. Key words: α-aminonitrile / α-aminoamide / enantioselective hydration / polamer-supported catalysis / ketonic resins
