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. 2011 Oct 4;50(41):9655-9.
doi: 10.1002/anie.201103145. Epub 2011 Jul 12.

Total synthesis of (+)-gliocladin C enabled by visible-light photoredox catalysis

Laura Furst  1 , Jagan M R Narayanam, Corey R J Stephenson
Affiliations

Total synthesis of (+)-gliocladin C enabled by visible-light photoredox catalysis

Laura Furst et al. Angew Chem Int Ed Engl. .
No abstract available

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Figures

Figure 1
Figure 1
Representative examples of cytotoxic and antibiotic C3–C3′ bisindole alkaloids.[6]
Scheme 1
Scheme 1
Retrosynthesis of gliocladin C (1; top) and visible-light-mediated C–C bond formation (bottom).
Scheme 2
Scheme 2
Visible-light-mediated coupling of bromopyrroloindoline 9 with indoles enables selective access to both C2′- and C3′-substituted bisindoles. Boc = tert-butyloxycarbonyl.
Scheme 3
Scheme 3
a) CbzCl, NaOH, Bu4NHSO4, CH2Cl2, 12 h; b) NBS, PPTS, CH2Cl2, 23°C, 12 h, 91% (two steps); c) MeNH2, THF, 23°C, 3 d, 87%; d) [Ru(bpy)3Cl2] (1.0 mol%), Bu3N (2 equiv), 15 (5 equiv), DMF, blue LEDs, 12 h, 82%; e) [Rh(Ph3P)3Cl] (1 equiv), xylenes, 140°C, 12 h, 86% or [Rh(CO)(Ph3P)2Cl] (20 mol%), dppp (44 mol%), DPPA (2 equiv), xylenes, 140°C, 85%; f) CbzCl, NaOH, Bu4NHSO4, CH2Cl2, 12 h, 98%; g) TMSI, CH3CN, 0°C, 1 h, 91%. Cbz = benzyloxycarbonyl; DMF = N,N′-dimethylformamide; DPPA = diphenylphosphoryl azide; dppp = 1,3-bis(diphenylphosphino)propane; LED = light-emitting diode; NBS = N-bromosuccinimide; PPTS = pyridinium p-toluenesulfonate; THF = tetrahydrofuran; TMS = trimethylsilyl.
Scheme 4
Scheme 4
a) NBS, CH2Cl2, DBU, 23°C, 99%; b) ClCOCO2Et, Et3N, 150°C, microwaves, 0.5 h, 76% (90% conversion, two cycles); c) BCl3, CH2Cl2, −78 °C to 23°C, 12 h, 80%. DBU = 1,8-diazabicyclo-[5.4.0]undec-7-ene.
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References

    1. a) Bisindole Alkaloids“: Cordell GA, Saxton JE. In: The Alkaloids: Chemistry and Physiology. Manske RHF, Rodrigo RGA, editors. Vol. 20. New York: Academic Press; 1981. pp. 3–294. b) ”Chemistry and Reactions of Cyclic Tautomers of Tryptamines and Tryptophans“: Hino T, Nakagawa M. In: The Alkaloids: Chemistry and Pharmacology. Brossi A, editor. Vol. 34. New York: Academic Press; 1989. pp. 1–75. c) ”Alkaloids from the Medicinal Plants of New Caledonia“: Sévenet T, Pusset J. In: The Alkaloids: Chemistry and Pharmacology. Cordell GA, editor. Vol. 48. New York: Academic Press; 1996. pp. 58–59.

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