78821-96-2

Upstream product

• 53153-53-0 d,l-Bi(3,5,5-trimethyl-2-oxomorpholin-3-yl) 
• 64040-81-9 bi(7-deoxyaklavinon-7-yl) 
• 57576-44-0 aclacinomycin A 
• 80173-04-2 methyl(9-RS,10-SR)-9-ethyl-6,9-dihydroxy-4-methoxy-5,12-dioxo-5,7,8,9,10,12-hexahydronaphthacene-10-carboxylate 
• 80173-04-2 c-2-Ethyl-1,2,3,4,6,11-hexahydro-t-2,5-dihydroxy-7-methoxy-6,11-dioxo-r-1-naphthacencarbonsaeure-methylester 
• 95456-09-0 3-acetyl-1,5-dimethoxy-4-methoxymethoxynaphthalene 
• 88365-13-3 9,10-Dihydro-4-hydroxy-5-methoxy-9,10-dioxo-3-(3-oxopentyl)-2-anthracencarbonsaeure 
• 88365-12-2 1-Hydroxy-3-(hydroxymethyl)-8-methoxy-2-(3-oxopentyl)-9,10-anthrachinon 
• 74188-46-8 4,5-Dihydroxy-9,10-dioxo-3-(3-oxopentyl)anthracene-2-acetic Acid, Methyl Ester 
• 135106-36-4 4-Hydroxy-5,8-dihydro-5,8-dioxo-3-(3-oxopentyl)-naphthaleneactic Acid, Methyl Ester 
• 97453-40-2 [9-(tert-Butyl-dimethyl-silanyloxy)-10-hydroxy-5-methoxy-4-oxo-3-(3-oxo-pentyl)-1,2,3,4-tetrahydro-anthracen-2-yl]-acetic acid methyl ester 
• 89101-88-2 methyl (6a-SR,9-RS,10-RS,10a-RS)-9-ethyl-12-t-butyldimethylsilyloxy-5,9-dihydroxy-4-methoxy-6-oxo-6,6a,7,8,9,10,10a,11-octahydronaphthacene-10-carboxylate 
• 89101-85-9 methyl 4-(1'-t-butyldimethylsilyloxy-4'-hydroxy-5'-methoxy-3'-(5''-oxoheptanoyl)-naphth-2'-yl)-2-butenoate 
• 95455-97-3 methyl 4-(4'-hydroxy-5'-methoxy-1'-oxo-3'-(5''-oxoheptanoyl)-1',2'-dihydronaphth-2'-yl)-2-butenoate 

Downstream Products

• 16234-96-1 t-2-Ethyl-1,2,3,4,6,11-hexahydro-c-2,t-4,5,7-tetrahydroxy-6,11-dioxo-r-1-naphthacencarbonsaeure-methylester 
• 16234-96-1 (+/-)-Aklavinon-I 
• 16234-96-1 (+/-)-7-epiaklavinone 
• 78821-97-3 (+/-)-aklavinone 
• 1055-56-7 Bisanhydroaklavinon 

Relevant academic research and scientific papers

SYNTHESES OF (+/-)-AKLAVINONES. APPLICATION OF THE STEREOCONTROLLED "ZIPPER" BICYCLO-CYCLIZATION REACTION

Efficient syntheses of (+/-)-aklavinones; (+/-)-aklavinone (1), (+/-)-auramycinone (2), and (+/-)-13-methylaklavinone (3), are described.A key process of the tetracyclic ring construction in these syntheses is a stereocontrolled "zipper" bicyclo-cyclizati

Spectroscopic and Kinetic Evidence for the Tautomer of 7-deoxyalklavinone as an Intermediate in the Reductive Coupling of Aclacinomycin A

Reduction of aclacinomycin A (7) with an excess of dl-bi(3,5,5-trimethyl-2-oxomorpholin-3-yl) (11) in Trizma-buffered methanol solvent in the absence of oxygen gave 7-deoxyalkavinone (8), bi(7-deoxyalkavinon-7-yl) (9), 5,6-dihydro-3,5,5-trimethyl-1,4-oxazin-2-one (12), and 3,5,5-trimethyl-2-oxomorpholine (13).The reducing agent was 3,5,5-trimethyl-2-oxomorpholin-3-yl (5) resulting from bond homolysis of 11.The relative yields of 8 and 9 were a function of the initial concentrations of 7 and 11 and the reaction time.The semiquinone 15 of 7 was observed as anintermediate by EPR spectroscopy.Uv-visible spectroscopic monitoring revealed the formation of the tautomer 14 of 7-deoxyalklavinone as a second intermediate in the formation of both 8 and 9.The tautomer showed absorption at 350 and 548 nm.Reaction of 9 with 11 resulted in reductive cleavage of 9 to 8 and disproportionation of 11 to 12 and 13.The mechanism proposed for the reduction of 7 is shown in Scheme III and includes protonation of 14 to give 8 and coupling of 14 followed by oxidation with 12 to give 9.The decay of the tautomer absorption followed mixed kinetics, first and second order in 14.Nonlinear least-squares analysis of the decay gave a pseudo-first-order rate constant for protonation equal to 3.36x10-3s-1 and a second-order rate constant for coupling equal to approximately 180 M-1s-1.The tautomer 14 of 7-deoxyalklavinone is protonated in buffered methanol 15 times slower than the tautomer 6 of 7-deoxydaunomycinone, thus allowing the coupling reaction to take place.The difference in reactivity of the tautomers may be relevant to the tumorresponse and toxicity of the two anthracyclines.

An Efficient Total Synthesis of (+/-)-Aklavinone

An 11-step total synthesis of (+/-)-aklavinone from 1,3-cyclohexadione is reported.The key steps include a Diels-Alder condensation of 3 and 4 and the stereoselective aldol condensation of 21 to 22.The overall yield is ca. 13percent.