Abstract
An enantioselective route to the key intermediate leading to (+)-vernolepin, an antitumor
sesquiterpene, isolated from Vernonia hymenolepis, has been developed starting from the chiral building block having a bicyclo[3.2.1]octane
framework accessible by either enzymatic or catalytic kinetic resolution.
Key words
chiral building block - convex-face stereoselection - (+)-vernolepin precursor - antitumor
sesquiterpene - bicyclo[3.2.1]octenone
References
<A NAME="RY04802ST-1A">1a</A>
Kupchan SM.
Hemingway R.
Karin A.
J. Am. Chem. Soc.
1968,
90:
3596
<A NAME="RY04802ST-1B">1b</A>
Kupchan SM.
Hemingway R.
Werner D.
Karin A.
J. Org. Chem. Soc.
1969,
34:
3903
<A NAME="RY04802ST-2A">2a</A>
Grieco PA.
Nishizawa M.
Oguri T.
Burke SD.
Marinovic N.
J. Am. Chem. Soc.
1976,
98:
1612
<A NAME="RY04802ST-2B">2b</A>
Grieco PA.
Nishizawa M.
Oguri T.
Burke SD.
Marinovic N.
J. Am. Chem. Soc.
1977,
99:
5773
<A NAME="RY04802ST-3A">3a</A>
Danishefsky S.
Kitahara T.
Schuda PF.
Etheredge SJ.
J. Am. Chem. Soc.
1976,
98:
3028
<A NAME="RY04802ST-3B">3b</A>
Danishefsky S.
Kitahara T.
Schuda PF.
Etheredge SJ.
J. Am. Chem. Soc.
1977,
99:
6066
<A NAME="RY04802ST-3C">3c</A>
Danishefsky S.
Kitahara T.
Schuda PF.
Etheredge SJ.
J. Am. Chem. Soc.
1977,
99:
6066
For racemic syntheses, see:
<A NAME="RY04802ST-4A">4a</A>
Kieczykowski GR.
Quesada ML.
Schlessinger RH.
J. Am. Chem. Soc.
1978,
100:
1938
<A NAME="RY04802ST-4B">4b</A>
Kieczykowski GR.
Quesada ML.
Schlessinger RH.
J. Am. Chem. Soc.
1980,
102:
782
<A NAME="RY04802ST-4C">4c</A>
Isobe M.
Iio M.
Kawai T.
Goto T.
J. Am. Chem. Soc.
1978,
100:
1940
<A NAME="RY04802ST-4D">4d</A>
Iio M.
Isobe M.
Kawai T.
Goto T.
J. Am. Chem. Soc.
1979,
101:
6076
<A NAME="RY04802ST-4E">4e</A>
Zutterman F.
De Wilde H.
Mijngheer R.
De Clercq P.
Vandewalle M.
Tetrahedron
1979,
35:
2389
<A NAME="RY04802ST-4F">4f</A>
Wakamatsu T.
Hara H.
Ban Y.
J. Org. Chem.
1985,
50:
10
For a enantiocontrolled synthesis, see:
<A NAME="RY04802ST-5A">5a</A>
Kondo K.
Sodeoka M.
Mori M.
Shibasaki M.
Tetrahedron Lett.
1993,
34:
4219
<A NAME="RY04802ST-5B">5b</A>
Ohrai K.
Kondo K.
Sodeoka M.
Shibasaki M.
J. Am. Chem. Soc.
1994,
116:
11737
<A NAME="RY04802ST-6">6</A>
Nagata H.
Miyazawa N.
Ogasawara K.
Org. Lett.
2001,
3:
1737
<A NAME="RY04802ST-7">7</A>
Hanada K.
Miyazawa N.
Naagata H.
Ogasawara K.
Synlett
2002,
125
<A NAME="RY04802ST-8">8</A>
Miyazawa, N.; Tosaka, A.; Hanada, K.; Ogasawara, K. to be published.
<A NAME="RY04802ST-9">9</A>
Nagata H.
Miyazawa N.
Ogasawara K.
Chem. Commun.
2001,
1094
<A NAME="RY04802ST-10">10</A>
Still WC.
J. Am. Chem. Soc.
1978,
100:
1481
<A NAME="RY04802ST-11">11</A>
Nagata H.
Kawamura M.
Ogasawara K.
Synthesis
2000,
1825
<A NAME="RY04802ST-12">12</A>
Horiguchi Y.
Matsuzawa S.
Nakamura E.
Kuwajima I.
Tetrahedron Lett.
1986,
27:
4025
<A NAME="RY04802ST-13">13</A>
Wege PM.
Clark RD.
Heathcock CH.
J. Org. Chem.
1976,
41:
3144
<A NAME="RY04802ST-14">14</A>
Heathcock CH.
Graham SL.
Pirrung MC.
Plavac F.
White CT.
The Total Synthesis of Natural Products
Vol. 5:
ApSimon J.
Wiley-Interscience;
New York:
1993.
p.93-107
<A NAME="RY04802ST-15">15</A>
Fetizon M.
Golfier M.
Compt. Rend. (C)
1968,
267:
900
<A NAME="RY04802ST-16">16</A>
Sharpless KB.
Lauer RF.
Terenishi Y.
J. Am. Chem. Soc.
1973,
95:
6137
<A NAME="RY04802ST-17">17</A>
Trost BM.
Salzmann TN.
J. Am. Chem. Soc.
1973,
95:
6840
<A NAME="RY04802ST-18">18</A>
Ito Y.
Hirao T.
Saegusa T.
J. Org. Chem.
1978,
43:
1011
<A NAME="RY04802ST-19">19</A>
Nicolaou KC.
Zhong Y.-L.
Baran PS.
J. Am. Chem. Soc.
2000,
122:
7596
<A NAME="RY04802ST-20">20</A>
Matsumura R.
Suzuki T.
Hagiwara H.
Hashi T.
Ando M.
Tetrahedron Lett.
2001,
42:
1543