New chiral ligands from myrtenal and caryophyllene for asymmetric oxydation of sulfides catalyzed by metal complexes

Khomenko, T. M.; Salomatina, Oksana V.; Kurbakova, S. Yu.; Ильина, И. В.; Волчо, К. П.; Комарова, Н. И.; Корчагина, Д. В.; Salakhutdinov, N. F.; Tolstikov, A. G.

doi:10.1134/s1070428006110091

Cited by 37 publications

(34 citation statements)

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“…28.28 (q, С(10)); 66.01 (t, С(11)); 160.93 (d, С(12)); 118.41 (s, С(13)); 163.41 (s, С(14)); 117.92 (d, С(15)); 132.50 (d, С(16)); 117.40 (d, С(17)); 131.63 (d, С(18)). Found: m/z 287.18944 [M] + .…”

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confidence: 98%

New chiral Schiff bases derived from (+)- and (−)-α-pinenes in the metal complex catalyzed asymmetric oxidation of sulfides

et al. 2008

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New chiral Schiff bases were derived from (+) and (-) α pinenes for the first time. Coordi nated to vanadium ions, they can be used as ligands in catalytic oxidation of sulfides into chiral sulfoxides. Conditions for the asymmetric oxidation of thioanisole to methyl phenyl sulfoxide in optical purity up to 32% were found. Variation of substituents in the ligand has a significant effect not only on enantioselectivity of the reaction, but also on absolute configuration of the sulfoxide formed.Chiral sulfoxides belong to important class of organic compounds, widely used in asymmetric synthesis. 1-3 In addition, compounds, containing asymmetric sulfoxide group, were isolated from a number of natural sourses, as well as biologically active sulfoxides of a certain configu ration were found. 4-7 All the enumerated facts stimulate elaboration of efficient methods for the synthesis of chiral sulfoxides, among which an asymmetric oxidation of prochiral sulfides, in particular, in the presence of vana dium containing metal complex systems, 8 seems to be the most reasonable.Vanadium complexes with chiral Schiff bases, obtained from cyclohexane 1,2 diamine, were first used for asym metric oxidation of aryl methyl sulfides with cumene hy droperoxide. 9 The yields of sulfoxides were good, and their enantiomeric excess (ее) reached 40%. Later, 10 it was found that application of vanadium complexes with ligands 1a,b, synthesized from the corresponding salicyl aldehydes and optically active β aminoalcohol, in combi nation with aqueous hydrogen peroxide as the oxidant allows one to obtain sulfoxides from alkyl aryl sulfides in good yields (up to 94%) and acceptable enantioselectivity (usually ее was 50-70%). It is necessary to note the simplicity in conducting the experiment with participation of these systems as compared with the trials carried out in the presence of homogeneous catalytic complexes on the * Dedicated to Academician G. A. Tolstikov in honor of his 75th anniversary.

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confidence: 98%

New chiral Schiff bases derived from (+)- and (−)-α-pinenes in the metal complex catalyzed asymmetric oxidation of sulfides

et al. 2008

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“…[2][3][4] Recently, 5 we found that the storage of (-)-cis-verbenol epoxide 1 on natural montmorillonite askanite-bentonite clay unexpectedly formed trans-diol 2 with a p-menthane framework as the major product (47%). Hydroxyketone 3, which had been obtained before as the major product of this reaction in the presence of ZnBr 2 , 6 was isolated in minor quantities (5%) (Scheme 1).…”

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Unusual α-hydroxyaldehyde with a cyclopentane framework from verbenol epoxide

Ardashov

Ильина

Корчагина

et al. 2007

Mendeleev Communications

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“…We used (1R)-(-)-myrtenal as a model system because some of its derivatives are good chiral auxiliaries that induce high enantiomeric excess because of the conformational restriction that is present in the bicyclic system [12][13][14][15][16]. Results of the addition of 4 -MeO-, 4 -Cl-or 4 -F-PhMgBr to myrtenal in the presence or absence of bismuth(III) nitrate at three temperatures (0°C, 25°C and reflux) are listed in Table 1.…”

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The First Synthesis of p-Cl- and p-F-Phenylverbenene

Contreras-Celedón¹,

Chacón-Garcı́a

2008

TOOCJ

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Abstract:The first synthesis of 4´-X-phenylverbenene (X = F and Cl) via reaction of myrtenal with 4 -X phenylmagnesium bromide and Bi(NO 3 ) 3 is described. Verbenene is formed due to the electron-withdrawing effect of the 4 -electronegative group, either fluorine or a Cl-Bi complex.Keywords: Myrtenal, verbenene, bismuth nitrate, pinane, lewis acid.In recent years, bismuth compounds have attracted great interest in organic synthesis. Although their chemistry is not well known, bismuth salts have been widely used as Lewis acids to catalyze numerous reactions, mainly functional group deprotections, oxidations, reductions, rearrangements and C-C bond formation [1]. The last of these reactions can be achieved by Friedel-Crafts acylation, aldolic and Knoevenagel condensations, Diels-Alder cycloaddition, and Michael addition, to mention just a few possibilities [2]. Recently, bismuth has also been used in the chemistry of natural products [3]. Studies on the chemistry of natural products of pinene derivatives have increased in recent years because of the wide biological activity that this group of compounds presents. One of these derivatives is verbenene 2 (Fig. 1), which is found as a secondary metabolite in many medicinal plants and has been investigated as a beetle attractor [4,5]. Verbenene has also been used in the study of cycloadditions on account of its restricted stereochemistry and can also be viewed as a precursor in the formal synthesis of verbenone, which can provide a possible starting point in the synthesis of the A ring of taxol and other interesting compounds [6][7][8][9][10]. Verbenene has been synthesized through an electron transfer from -or -pinene to 2,3,5,6-tetrachlorobenzoquinone on sensitized irradiation where a radical cation rapidly deprotonates to give verbenene with retention of chirality [11]. To study the mechanism of bismuth-catalyzed additions to double bond carbonyl-activated systems, in the present work we examined the addition of Grignard reagents to myrtenal 1 catalyzed by Bi(NO 3 ) 3 . We found no difference in diastereoselectivity, but surprisingly observed the production of phenylverbenenes 3c and 3d in good yield when 4 -Cl-or 4 -F-phenylmagnesium bromide was added at 0°C (Scheme 1). Under the same conditions but in the presence of methyl iodide, alcohols 4 and 5 (c and d) give 3 (c and d respectively) in 98% yield (Scheme 1). RESULTS AND DISCUSSIONWe used (1R)-(-)-myrtenal as a model system because some of its derivatives are good chiral auxiliaries that induce high enantiomeric excess because of the conformational restriction that is present in the bicyclic system [12][13][14][15][16]. Results of the addition of 4 -MeO-, 4 -Cl-or 4 -F-PhMgBr to myrtenal in the presence or absence of bismuth(III) nitrate at three temperatures (0°C, 25°C and reflux) are listed in Table 1.The results show no significant difference in diastereoselectivity among the various reactions, and the bismuth salt does not have any effect on the reaction. Although no significant diastereoisomeric excess w...

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New chiral ligands from myrtenal and caryophyllene for asymmetric oxydation of sulfides catalyzed by metal complexes

Cited by 37 publications

References 20 publications

New chiral Schiff bases derived from (+)- and (−)-α-pinenes in the metal complex catalyzed asymmetric oxidation of sulfides

New chiral Schiff bases derived from (+)- and (−)-α-pinenes in the metal complex catalyzed asymmetric oxidation of sulfides

Unusual α-hydroxyaldehyde with a cyclopentane framework from verbenol epoxide

The First Synthesis of p-Cl- and p-F-Phenylverbenene

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