An efficient and stereoselective dearylation of asarinin and sesamin tetrahydrofurofuran lignans to acuminatolide by methyltrioxorhenium/H(2)O(2) and UHP systems.
The synthesis of stereoisomers of acuminatolide is rare and requires complex and time-consuming multistep procedures. Asarinin (1) and sesamin (2), two diasteromeric tetrahydrofurofuran lignans, are efficiently mono-dearylated by methyltrioxorhenium (MTO, I) and hydrogen peroxide (H2O2) or urea hydrogen peroxide adduct (UHP) as primary oxidant to give (-)-(7R,8'R,8R)-acuminatolide (3A) and (+)-(7S,8R,8'R)-acuminatolide (3B), respectively, in high yield and diastereoselectivity (de >98%). The oxidation of 1 was also performed with novel heterogeneous catalysts based on the heterogenation of MTO on poly(4-vinylpyridine) and polystyrene resins. In these latter cases 3A was obtained with a different yield and selectivity depending on the physical-chemical properties of the support. Cytotoxic effects of 3A and 3B in mammalian cell lines in vitro are also reported.
Saladino
Raffaele
R
Dipartimento di Agrobiologia ed Agrochimica, Università della Tuscia, via S. Camillo de Lellis, snc, 01100 Viterbo, Italy. Saladino@unitus.it
Fiani
Cinzia
C
Crestini
Claudia
C
Argyropoulos
Dimitris S
DS
Marini
Stefano
S
Coletta
Massimiliano
M
D000818:Animals; D000970:Antineoplastic Agents / Q000737:chemistry* / Q000302:isolation & purification / Q000494:pharmacology; D004149:Dioxoles / Q000737:chemistry* / Q000302:isolation & purification / Q000494:pharmacology; D004354:Drug Screening Assays, Antitumor; D006801:Humans; D017705:Lignans / Q000737:chemistry* / Q000302:isolation & purification / Q000494:pharmacology; D051379:Mice; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D010084:Oxidation-Reduction; D012211:Rhenium / Q000737:chemistry; D013237:Stereoisomerism; D032106:Zanthoxylum / Q000737:chemistry*
D000970:Antineoplastic Agents; D004149:Dioxoles; D017705:Lignans; D009942:Organometallic Compounds; C517583:acuminatolide; D012211:Rhenium; C411866:methyltrioxorhenium VII; C054125:sesamin