Naturstoffchemie, 174. Mitt. [1]: Oxidation von Acronycin mit Kaliumpermanganat

Abstract

7-on (2), 1-Hydroxy-6-methoxy-3,3,12-trimethyl-lH-pyrano[2,3-c]acridin-2,7(3H,12H)-dion (3) und 1-Hydroxy-6-methoxy-3,3,12 1S-cis)-l,2,3,12-tetrahydro-l,2-dihydroxy-6-methoxy-3,3,12-trimethyl-7H-pyrano[2,3-c]acridine-7-one (2), 1-hydroxy-6-methoxy-3,3,12-trimethyl-lH-pyrano-[2,3-c]acridine-2,7(3H,12H)-dione (3) and 1-hydroxy-6-methoxy-3,3,12-trimethyl-!-(2-oxopropyl)-1H-pyrano [2,3-c] acridine-2,7(3 H,l 2H)-dione (4).

Quinoline, quinazoline and acridone alkaloids

“…80 The three products were the hydroxyketone 157, the cisdiol 158 and the unusual condensation product 159. This result corrects an earlier report 81 in which the regiochemistry of products 157 and 159 was transposed (cf. ref.…”

Synthesis and Cytotoxic and Antitumor Activity of Esters in the 1,2-Dihydroxy-1,2-dihydroacronycine Series

“…The recent isolation in our laboratory of acronycine epoxide ( 13 ) from several New-Caledonian Sarcomelicope species led us to consider this compound as a possible active metabolite of acronycine in vivo . The high reactivity of that epoxide and the difficulties encountered by us and by others in the attempts toward its synthesis are consistent with this hypothesis. In addition, this assumption should explain the importance of the 1,2-double bond on the pyran ring to observe cytotoxic activty in the acronycine series.…”

Synthesis and Biological Activity of Esters in the trans-1,2-Dihydroxy-1,2-dihydroacronycine Series

“…The trans -1,2-dihydroxy-1,2-dihydroacronycine ( 3 ) recently isolated from the leaves of Sarcomelicope glauca was a suitable candidate for esterification reactions. Treatment of acronycine ( 1 ) with KMnO 4 , in Me 2 CO−H 2 O solution gave three products: 1-oxo-2-hydroxy-1,2-dihydroacronycine ( 4 ), cis -1,2-dihydroxy-1,2-dihydroacronycine ( 5 ), and 1-oxo-2-hydroxy-2-acetonyl-1,2-dihydroacronycine ( 6 ) (Scheme ). It is interesting to note that the same reaction was explored recently; the same compounds (identical spectral and physical data) were obtained, but the structure elucidation was erroneous for compounds 4 and 6 , which were depicted as 7 and 8 , respectively.…”

“…Treatment of acronycine ( 1 ) with KMnO 4 , in Me 2 CO−H 2 O solution gave three products: 1-oxo-2-hydroxy-1,2-dihydroacronycine ( 4 ), cis -1,2-dihydroxy-1,2-dihydroacronycine ( 5 ), and 1-oxo-2-hydroxy-2-acetonyl-1,2-dihydroacronycine ( 6 ) (Scheme ). It is interesting to note that the same reaction was explored recently; the same compounds (identical spectral and physical data) were obtained, but the structure elucidation was erroneous for compounds 4 and 6 , which were depicted as 7 and 8 , respectively. We were able to determine unambiguously the position of the carbonyl group for the above compounds on the basis of spectroscopic and chemical methods.…”

“…In a second step, homobenzylic deoxygenation afforded the 1-oxo-1,2dihydroacronycine (10). If the carbonyl group is in the 2 position, the deoxygenation reaction should lead to the known 2-oxo-1,2-dihydroacronycine (11). 12 The signals of 1 H-and 13 C-NMR spectra for compounds 10 and 11 were unambiguously assigned using 13 C-1 H HETCOR and HMBC experiments (Figure 1).…”