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16-epinormacusine B
10, R1 = H, R2 =CH2OH
normacusine B
21, R1 = CH2OTIPS, R2 = H
22, R1 = H, R2 = CH2OTIPS
b
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c
CH3
N
Cbz
N
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H
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H
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25, R1 = CH2OTIPS, R2 = H
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23, R1 = CH2OTIPS, R2 = H
24, R1 = H, R2 = CH2OTIPS
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vobasinediol
1, R1 = CH2OH, R2 = H
affinine
4, R1 = H, R2 = CH2OH
16-epivobasinediol
2, R1 = H, R2 = CH2OH
16-epiaffinine
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Scheme 4. Reagents and conditions: (a) TIPSOTf, 2,6-lutidine, CH2Cl2, 0 °C, 2 h, 21:
85%, 22: 82%; (b) Cbz–Cl, THF–H2O, Na2CO3, 23: 77%, 24: 71%; (c) LiAlH4, THF, rt,
12 h, 25: 78%, 26: 70%; (d) TBAF, THF, 0 °C, 3–4 h, 3: 90%, 4: 85%; (e) MnO2, CH2Cl2,
1: 92%, 2: 82%.
the Cbz–Cl mediated scission were the key steps in these synthe-
ses. The ability to stereospecifically prepare either epimer at
C(16) at will was gratifying because the corresponding b-axial
aldehyde is the thermodynamically less stable isomer. This ap-
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functionalized sarpagine-related indole alkaloids.
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Acknowledgments
We thank NIMH (in part) and the Research Growth Initiative of
the University of Wisconsin-Milwaukee for the support of this
work.
References and notes
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