A practical procedure for the preparation of O-methyl substituted 3a,8-dialkyl-2-oxofuroindolines is described. Reductive lactonization of the corresponding oxindol-3-ylacetic acids provides a route for the formation of this class of compounds. Further transformation of 2-oxofuroindolines into 2-oxopyrrolidinoindolines, and then to pyrrolidinoindolines demonstrates their versatility as key intermediates in natural products synthesis. The results of single-crystal X-ray crystallographic analyses are given for five of the studied compounds.
JossangA, JossangP, HadiHA, SevenetT, BodoB. (1991) Horsfiline, an oxindole alkaloid from Horsfieldia superba. Journal of Medicinal Chemistry, 56, 6527–6530.
2.
CuiC-B, KakeyaH, OkadaG, OnoseR, OsadaH. (1996) Novel mammalian cell cycle inhibitors, tryprostatins A, B and other diketopiperazines produced by Aspergillus fumigatus: I. Taxonomy, fermentation, isolation and biological properties. Journal of Antibiotics, 49, 527–533
3.
CuiC-B, KakeyaH, OsadaH. (1977) Novel mammalian cell cycle inhibitors, cyclotroprostatins A–D, produced by Aspergillus fumigatus, which inhibit mammalian cell cycle at G2/M phase. Tetrahedron, 53, 59–72
4.
UsuiT, KondohM, CuiC-B, MayumiT, OsadaH. (1998) Tryprostatin A, a specific and novel inhibitor of microtubule assembly. Biochemical Journal, 333, 543–548.
5.
HiromitsuT, YuhkoM, MarikoK, NorioA, SumphanW, DhavadeeP, Shin-ichiroS. (1994) Two new iridoids from the leaves of Gelsemium elegans Benth, in Thailand. Natural Product Letters, 5, 15–20.
6.
DuXB, DaiYH, ZhangCL, LuSL, LiuSL. (1982) Studies on the gelsemium alkaloids. I. The structure of gelsenicine. Huaxue Xuebao, 40, 1137–1141
7.
YanJS, ChenYW. (1983) Chemical studies on the alkaloids of Hu Man Teng (Gelsemium elegans Benth). I. Isolation of the alkaloids and the structure of humantenmine. Yaoxue Xuebao, 18, 104–112
8.
TakayamaH, TominagaY, KitajimaM, AimiN, SakaiS. (1994) First synthesis of the novel gelsemium alkaloids, gelselegine, gelsenicine, and gelsedine using a biomimetic approach. Journal of Organic Chemistry, 59, 4381–4385
9.
KogureN, IshiiN, KitajimaM, WongseripipatanaS, TakayamaH. (2006) Four novel gelsenicine-related oxindole alkaloids from the leaves of Gelsemium elegans Benth. Organic Letters, 8, 3085–3088.
10.
ZhangZ, DiY-T, WangY-H, ZhangZ, MuS-Z, FangX, ZhangY, TanC-j, ZhangQ, YanX-H, GuoJ, LiC-S, HaoX-J. (2009) Gelegamines A-E: five new oxindole alkaloids from Gelsemium elegans. Tetrahedron, 65, 4551–4556.
11.
For recent reviews on the properties of oxindoles and synthetic routes, see: (a) PeddibhotlaS. (2009) 3-Substituted-3-hydroxy-2-oxindole, an emerging new scaffold for drug discovery with potential anti-cancer and other biological activities. Current Bioactive Compounds, 5, 20–38
12.
GallifordCV, ScheidtKA. (2007) Pyrrolidinyl-spirooxindole natural products as inspirations for the development of potential therapeutic agents. Angewandte Chemie International Edition, 46, 8748–8758
13.
TrostBM, BrennanMK. (2009) Asymmetric syntheses of oxindole and indole spirocyclic alkaloid natural products. Synthesis, 3003–3025.
14.
Morales-RíosMS, Suárez-CastilloOR. (2008) Synthesis of marine indole alkaloids from Flustra foliacea. Natural Product Communications, 3, 629–642
15.
StevenA, OvermanLE. (2007) Total synthesis of complex cyclotryptamine alkaloids: stereocontrolled construction of quaternary carbon stereocenters. Angewandte Chemie International Edition, 46, 5488–5508.
16.
Morales-RíosMS, Suárez-CastilloOR, Trujillo-SerratoJJ, Joseph-NathanP. (2001) Total synthesis of five indole alkaloids from the marine bryozoan Flustra foliacea. Journal of Organic Chemistry, 66, 1186–1192
17.
Rivera-BecerrilE, Joseph-Nathan P, Pérez-AlvarezVM, Morales-RíosMS. (2008) Synthesis and biological evaluation of (-)- and (+)-debromoflyustramine B and its analogues as selective butyrylcholinesterase inhibitors. Journal of Medicinal Chemistry, 51, 5271–5284
18.
Morales-RíosMS, Santos-SánchezNF, Mora-PérezY, Joseph-NathanP. (2004) Synthesis of isotope labeled Me(3a)-13C-physostigmine and debromoflustramine B. Heterocycles, 63, 1131–1142
19.
Morales-RíosMS, Rivera-BecerrilE, Joseph-NathanP. (2005) Synthesis of (3aS-cis)-(-)- and (3aR-cis)-(+)-debromoflustramine B. Tetrahedron: Asymmetry, 16, 2493–2499.
20.
Morales-RíosMS, Rivera-BecerrilE, González-JuárezDE, García-VázquezJB; Trujillo-SerratoJJ, Hernández-BarragánA, Joseph-NathanP. (2011) Synthesis of pyrrolidinoindolines from 2-(2-oxo-3-indolyl)acetates: scope and limitations. Natural Product Communications, 6, 457–464.
21.
Rivera-BecerrilE, Pérez-HernándezN, Joseph-NathanP, Morales-RíosMS. (2006) Structural characterization of isomeric methyl 2-(2-oxo-3-indolyl)acetate and methyl 1-(2-oxo-4-quinolyl)formate. Heterocycles, 68, 1459–1466
22.
Morales-RíosMS, Martínez-GaleroNX, Loeza-CoriaM, Joseph-NathanP. (1995) Mechanistic studies of the ring expansion reaction of isatylidenes to quinolines. Journal of Organic Chemistry, 60, 6194–6197
23.
Suárez-CastilloOR, Bautista-HernándezCI, Sánchez-ZavalaM, Meléndez-RodríguezM, Sierra-ZentenoA, Morales-RíosMS, Joseph-NathanP. (2012) Microwave-assisted synthesis of 3,1-benzoxazin-2-ones from 3-hydroxyoxindoles. Heterocycles, 85, 2147–2171.
24.
Prepared by hydrolysis of 5-methoxyindole-3-acetonitrile with aqueous methanolic potassium hydroxide. SzmuszkoviczJ, AnthonyWC, HeinzelmanRV. (1960) N-Acetyl-5-methoxytryptamine. Journal of Organic Chemistry, 25, 857–859.
25.
Prepared by Fischer indolization of N-benzyl-p-methoxyphenylhydrazone of ethyl 4-bromo-3-oxobutanoate fo10llowed by hydrolysis. JuliaM, LenziJ. (1962) Research in the indole series. IV. Preparation of 3-indolylacetic acid derivatives. Bulletin de la Société Chimique de France, 1051–1055.
26.
Pérez-AlvarezV, Morales-RíosMS, HongE, Joseph-NathanP. (1997) Synthesis of 3-amino-2-(3-indolyl)propanol and propanoate derivatives and preliminar cardiovascular evaluation in rats. Journal of Pharmacy and Pharmacology, 49, 246–252.
27.
AttenniB, FerrignoF, JonesP, IngenitoR, KinzelO, Bufi LlaugerL, Ontoria OntoriaJM, PescatoreG, RowleyM, ScarpelliR, SchultzC.Preparation of heterocycle derivatives as histone deacetylase inhibitors. PCT Int. Appl. 2006, 215 pp, WO 2006061638, A2, CAN 145:62907.
28.
SergeyevNM. (1990) In NMR Basic Principles and Progress, Vol. 22. DiehlP, FluckE, GüntherH, KosfeldR, SeeligJ.(Eds). Springer, Berlin. 58.
29.
ArndtF. (1943) Nitrosomethylurea. I. From methylamine hydrochloride. Organic Syntheses Collective, 2, 165–167.
