128261-64-3Relevant academic research and scientific papers
Preparation of optically active apoverbenone and verbenone from nopinone by use of the sulfenylation-dehydrosulfenylation method. Stability and reactivity attributable to absolute configuration at the sulfur atom in sulfoxides
Kosugi, Hiroshi,Ku, Jaseung,Kato, Michiharu
, p. 6939 - 6946 (2007/10/03)
Apoverbenone (4) and verbenone (5) in optically active forms are potentially useful compounds as the chiral source in enantioselective synthesis. Starting with (+)-nopinone (1), readily available from (-)-β-pinene, (+)-apoverbenone (4a) and (+)-verbenone (5a) were prepared in synthetically satisfactory overall yields, using commonly the sulfenylation-dehydrosulfenylation method directed toward construction of an enone function. This methodology could be applicable to preparation of their enantiomers (-)-4b and (-)-5b on starting with (-)-nopinone. While configuration of the phenylsulfinyl group in sulfoxides 10a, b, and 18a, b were assigned by their NMR spectra and NOE correlations, absolute configurations at the sulfur atom were performed by comparison in 1H NMR spectra with their homologues whose absolute configurations are well-defined, that is, lOa with 13a, lOb with 13b, 18a with 19b, and 18b with 19a. As a result, it was proved that, in 3-(phenylsulfinyl)nopinones, thermodynamic stability of isomers is dependent on absolute configuration at the sulfur center; that is, the frans-isomer 10a possesses an Rs-phenylsulfinyl group and the a's-isomer 10b possesses an Ss-phenylsulfinyl group, and it was proved that, in (4R)-4methyl-3-(phenylsulfinyl)nopinones, both as-isomers 18a, b are stable, irrelevant with absolute configurations at the sulfur atom. In elimination of phenylsulfenic acid from sulfoxides 10 and 18, the use of purified sulfoxides was essential, because the competing Pummerer reaction proceeded to give 3-(phenylthio)verbenone (11) as a byproduct, when acidic contaminants were present. The sulfoxides 10a, b and 18a provided smoothly 4a and 5a, respectively, in a syn elimination manner, whereas 18b gave a mixture of decomposed products as a major part, probably because of instability of 18b to heat as well as because of its conformational requirement.
Efficient Synthesis of (1S,5S)-4-Alkyl-6,6-dimethylbicyclohept-3-en-2-ones from (1R,5S)-(+)-Nopinone and Preparation of Some Chiral Building Blocks Suitable for the Asymmetric Synthesis
Watanabe, Masataka,Awen, Bahlul Z.,Kato, Michiharu
, p. 3923 - 3927 (2007/10/02)
A general and convenient transformation of (1R,5S)-(+)-nopinone (1) into (1S,5S)-4-alkyl-6,6-dimethylbicyclohept-3-en-2-ones, i.e. (-)-verbenone (6a) as the simplest compound and its C(4)-alkyl homologs 6b-f, via (+)-apoverbenone (7) is developed and applied, starting with 6a,e, to the syntheses of (4R,5R)-1-acetoxy-4-isopropenyl-5-methyl-5-vinyl-1-cyclohexene (12a) and (4R,5S)- and (4R,5R)-1-acetoxy-5-(3-butenyl)-4-isopropenyl-5-methyl-1-cyclohexene (12b and 12c), in connection with a search for chiral building blocks suitable for the asymmetric synthesis.Preparation of 12a indicates the formal synthesis of the elemanoid sesquiterpenes (-)-β-elemenone and (-)-eleman-8β,12-olide
The Use of 4,4-Disubstituted Nopinones for Natural-Product Synthesis. Synthesis of Elemanoid Sesquiterpenes
Kato, Michiharu,Watanabe, Masataka,Vogler, Bernhard,Awen, Bahlul Z.,Masuda, Yoshiaki,et al.
, p. 7071 - 7076 (2007/10/02)
A general and convenient synthetic route to 4,4-disubstituted nopinones 14 from (+)-nopinone (1) is developed and applied to the asymmetric synthesis of some representative elemanoid sesquiterpenes.Phenylsulfenylation of 1 provided sulfide 6 in high yields.A convenient transformation of 6 to 3-(phenylsulfonyl)-4,4-disubstituted-nopinones 13 was accomplished by (i) m-CPBA oxidation of a sulfide compound followed by the Pummerer rearrangement and (ii) the conjugate addition of carbon nucleophiles to the resulting enones, 6 -> 8 -> 9 and 9 -> 10, 11 -> 13.Subsequent reductive desulfurization of the adducts 13 provided 14 in good overall yield from 1.Bicyclic ketones 14 are envisioned as promising intermediates for natural product synthesis.As examples, syntheses of two elemanoid sesquiterpenes, β-elemenone (16) and eleman-8β,12-olide (17) in optically active form from (1R,4S,5S)-4,6,6-trimethyl-4-vinylbicycloheptan-2-one (14a) were carried out.
A Key Intermediate for the Chiral Synthesis of Elemanoids. Synthesis of (+)-β-Elemenone
Kato, Michiharu,Vogler, Bernhard,Tooyama, Youichi,Yoshikoshi,Akira
, p. 151 - 154 (2007/10/02)
(1R,5S)-3-Phenylsulfenyl-6,6-dimethylbicycloheptanone obtained from (+)-nopinone was transformed into (1R,4S,5S)-4-methyl-4-vinylbicycloheptan-2-one, whose cyclobutane ring was cleaved with BF3*EtO2-Zn(OAc)2 in acetic anhydride to provide (4S,5S)-1-acetoxy-4-isopropenyl-5-methyl-5-vinyl-1-cyclohexene (5), the key intermediate, in a highly regio- and stereoselective manner.Regioselective introduction of a three-carbon unit to 5 with acetone followed by dehydration yielded (+)-β-elemenone.
