A highly efficient method for the formal synthesis of the natural product (±)-coerulescine 1 from tetrahydro-β-carboline 3, mediated by dimethyldioxirane (DMD), is described. Compound 15, the N9-demethylated precursor of 1, was prepared from 3 in 4 steps with an overall yield of 95%. The effect of electron withdrawing groups at the N2, N9 atoms of 3 was explored for the oxidative rearrangement step.
MartiC, CarreiraEM. (2003) Construction of spiro[pyrrolidine-3,3′-oxindoles] – Recent applications to the synthesis of oxindole alkaloids. European Journal of Organic Chemistry, 2209–2219
2.
ChangM-Y, PaiC-L, KungY-H. (2005) Synthesis of (±)-coerulescine and a formal synthesis of (±)-horsfiline. Tetrahedron Letters, 46, 8463–8465
3.
LizosDE,. MurphyJA. (2003) Concise synthesis of (±)-horsfiline and (±)-coerulescine by tandem cyclisation of iodoaryl alkenyl azides. Organic and Biomolecular Chemistry, 1, 117–122
4.
PetterssonM, KnueppelD, MartinSF. (2007) Concise, stereoselective approach to the spirooxindole ring system of citrinadin A. Organic Letters, 9, 4623–4626
WhiteJD, IhleDC. (2006) Tandem photocycloaddition-retro-Mannich fragmentation of enaminones. A route to spiropyrrolines and the tetracyclic core of koumine. Organic Letters, 8, 1081–1084
MiyakeFY, YakushijinK, HorneDA. (2004) Preparation and synthetic applications of 2-halotryptamines: synthesis of elacomine and isoelacomine. Organic Letters, 6, 711–713.
AndertonN, CockrumPA, ColegateSM, EdgarJA, FlowerK, GardnerD, WillingRI. (1999) (-)-Phalarine, a furanobisindole alkaloid from Phalaris coerulescens. Phytochemistry, 51, 153–157
11.
AndertonN, CockrumPA, ColegateSM, EdgarJA, FlowerK. (1999) Assessment of potential for toxicity of Phalaris spp. via alkaloid content determination: P. coerulescens, a case example. Phytochemical Analysis, 10, 113–118.
12.
JossangA, JossangP, HadiHA, SévenetT, BodoB. (1991) Horsfiline, and oxindole alkaloid from Horsfieldia superba. Journal of Organic Chemistry, 56, 6527–6530.
13.
SomeiM, NoguchiK, YamagamiR, KawadaY, YamadaK, YamadaF. (2000) Preparation and a novel rearrangement reaction of 1,2,3,4-tetrahydro-9-hydroxy-β-carboline, and their applications for the total synthesis of (±)-coerulescine. Heterocycles, 53, 7–10.
14.
KuehneME, RolandDM, HafterR. (1978) Studies in biomimetic alkaloid syntheses. 2. Synthesis of vincadifformine from tetrahydro-β-carboline through a secodine intermediate. Journal of Organic Chemistry, 43, 3705–3710.
15.
KornetMJ, ThioAP. (1976) Oxindole-3-spiropyrrolidines and –piperidines. Synthesis and local anesthetic activity. Journal of Medicinal Chemistry, 19, 892–898.
16.
LiC, ChanC, HeimannAC, DanishefskySJ. (2007) On the rearrangement of an azaspiroindolenine to a precursor to phalarine: mechanistic insights. Angewandte Chemie International Edition, 46, 1444–1447
17.
PellegriniC, WeberM, BorschbergH-J. (1996) Total synthesis of (+)-elacomine and (-)-isoelacomione, two hitherto unnamed oxindole alkaloids from Elaeagnus commutata. Helvetica Chimica Acta, 79, 151–168.
18.
Suárez-CastilloOR, Sánchez-ZavalaM, Meléndez-RodríguezM, Castelán-DuarteLE, Morales-RíosMS, Joseph-NathanP. (2006) Preparation of 3-hydroxyoxindoles with dimethyldioxirane and their use for the synthesis of natural products. Tetrahedron, 62, 3040–3051
19.
Suárez-CastilloOR, Sánchez-ZavalaM, Meléndez-RodríguezM, Aquino-TorresE, Morales-RíosMS, Joseph-NathanP. (2007) First total synthesis of (±)-flustraminol B. Heterocycles, 71, 1539–1551.
20.
CoreyPF, WardFE. (1986) Buffered potassium peroxymonosulfate-acetone epoxidation of α,β-unsaturated acids. Journal of Organic Chemistry, 51, 1925–1926.
21.
ShiehW-C, DellS, BachA, RepičO, BlacklockTJ. (2003) Dual nucleophilic catalysis with DABCO for the N-methylation of indoles. Journal of Organic Chemistry, 68, 1954–1957
22.
OukS, ThiébaudS, BorredonE. (2005) N-Methylation of nitrogen-containing heterocycles with dimethyl carbonate. Synthetic Communications, 35, 3021–3026
23.
TundoP, RossiL, LorisA. (2005) Dimethyl Carbonate as an Ambident Electrophile. Journal of Organic Chemistry, 70, 2219–2224.
24.
Suárez-CastilloOR, Contreras-MartínezYMA, Beiza-GranadosL, Meléndez-RodríguezM, Villagómez-IbarraJR, Torres-ValenciaJM, Morales-RíosMS, Joseph-NathanP. (2005) Conformational studies of N-carbomethoxy-2-alkoxyindolenines by dynamic NMR, crystallography, and molecular mechanics. Tetrahedron, 61, 8809–8820.
25.
Suárez-CastilloOR, Montiel-OrtegaLA, Meléndez-RodríguezM, Sánchez-ZavalaM. (2007) Cleavage of alkoxycarbonyl protecting groups from carbamates by t-BuNH2. Tetrahedron Letters, 48, 17–20.
26.
CossyJ, CasesM, Gomez PardoD. (1998) A convenient route to spiropyrrolidinyl-oxindole alkaloids via C-3 substituted ene-pyrrolidine carbamate radical cyclization. Tetrahedron Letters, 39, 2331–2332.
27.
StillWC, KahnM, MitraA. (1978) Rapid chromatographic technique for preparative separations with moderate resolution. Journal of Organic Chemistry, 43, 2923–2925.
28.
SheldrickGM. (1988) Programs for Crystal Structure Analysis (Release 97-2). Institut für Anorganische Chemie der Universität, University of Göttingen: Göttingen, Germany.
29.
FarrugiaLJ. (1999) WinGX suite for small-molecule single-crystal crystallography. Journal of Applied Crystallography, 32, 837–838.