A dihydropyrrolizinyl oxindole

NOESY

General procedure for synthesis of compounds 7a–7c from the three-component reaction of isatins, proline and aroylacrylic acids: A mixture of isatin (1.0 mmol), proline (1.0 mmol) and aroylacrylic acid (1.0 mmol) in 4.0 mL aqueous ethanol (1:3) was heated in an oil bath to reflux temperature for 15 min. The resulting precipitates were collected by filtration and washed with cold ethanol to give analytically pure products 7. 7a: orange powder, 22%, mp 215–216 °C. ¹H (500 MHz, DMSO-d₆) and ¹³C NMR (125 MHz, DMSO-d₆) data are given in Table 3. MS (m/z) (%): 462 (M⁺, 52), 435 (45), 405 (8), 353 (12), 317 (18), 289 (52), 208 (30), 173 (33), 127 (46), 75 (30), 41 (100); anal. calcd for C₂₁H₁₅BrСl₂N₂O (462.17): C 54.57; H 3.27; N 6.06; found: C 54.48; H 3.19; N 6.10.


The tentative mechanism for the formation of 7a is outlined in Scheme 3. First, the initially formed spiropyrrolizidine undergoes decarboxylation via ring opening of the spiro cycle. The subsequent enolization of the intermediate leads to the formation of the dihydropyrrolizinyl oxindole system.

Scheme 3: Tentative reaction mechanism for the decarboxylative cyclative rearrangement of the initial three-component product.

For assigning structures of byproducts we carried out the reaction of isatins 1, aroylacrylic acids 5 and proline in a boiling mixture of EtOH and water, which resulted in the formation and isolation of compounds 7a–7c (Scheme 2). The unexpected structure of rearranged product 7a was confirmed by ¹H, ¹³C and 2D NMR spectroscopy (Table 3).

Scheme 2: The synthesis of compounds 7a–7c.

Table 3: ¹³C and ¹H spectral data for compound 7a.

entry	functional group	13C	1H
		δ, ppm	δ, ppm	multiplicity	J, Hz
1	1-NH	–	10.59	s	–
2	2-CO	178.09	–	–	–
3	3-CH	45.33	4.56	s	–
4	3a-C (oxindole)	134.06	–	–	–
5	4-CH (oxindole)	127.55	7.05	s	–
6	5-C (oxindole)	113.56	–	–	–
7	6-CH (oxindole)	130.77	7.33	dd	8.1; 2.2
8	7-CH (oxindole)	111.57	6.80	d	8.1
9	7a-C (oxindole)	142.21	–	–	–
10	5-C	124.67	–	–	–
11	6-C	120.38	–	–	–
12	7-CH	99.69	5.30	s	–
13	7a-C	138.34	–	–	–
14	1-CH2	24.43	2.85–2.63	m	–
15	2-CH2	27.31	2.43–2.27	m	–
16	3-CH2	46.26	4.20–4.02, 3.90–3.70	m	–
17	1-C Ar	129.50	–	–	–
18	2-CH Ar	129.87	7.82	d	1.8
19	3-C Ar	133.12	–	–	–
20	4-C Ar	131.63	–	–	–
21	5-CH Ar	130.95	7.65	d	8.1
22	6-CH Ar	128.44	7.55	dd	8.2; 1.8

The main feature of the ¹³C spectra of compounds 7a–7c is the absence of the signal of the 3C-spiro nucleus. The ¹H NMR spectrum of compound 7a displays a singlet at 5.30 ppm for the 7-CH of the dihydropyrrolizinyl moiety, which shows a H,H-NOESY correlation with a singlet at 4.56 ppm (3-CH of the oxindole ring) and HMBCs with 7a-C at 138.34 ppm. The singlet at 4.56 ppm of 3-CH of the oxindole ring shows H,H-COSY and H,H-NOESY correlations with a singlet at 7.05 ppm of 4-CH (oxindole ring) and HMBCs with 2-CO at 178.09 ppm, 4-C at 127.55 ppm and 6-C at 120.38 ppm (Figure 7). The NH proton of the oxindole ring gives a singlet at 10.59 ppm.

Figure 7: The selected COSY, NOESY and HMBC correlations of the signals in the ¹H and ¹³C NMR spectra of compound 7a.

see................http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-10-8

The regioselective synthesis of spirooxindolo pyrrolidines and pyrrolizidines via three-component reactions of acrylamides and aroylacrylic acids with isatins and α-amino acids

Tatyana L. Pavlovskaya¹, Fedor G. Yaremenko^1,2, Victoria V. Lipson^1,2,3, Svetlana V. Shishkina¹, Oleg V. Shishkin^1,3, Vladimir I. Musatov¹ and Alexander S. Karpenko⁴

¹State Scientific Institution “Institute for Single Crystals” of National Academy of Sciences of Ukraine, 60, Lenin ave., Kharkov, 61178, Ukraine
²Antidiabetic Drug Laboratory, State Institution “V.J. Danilevsky Institute of Problems of Endocrine Pathology at the Academy of Medical Sciences of Ukraine”, 10, Artem St., Kharkov, 61002, Ukraine
³Organic Chemistry Department, V.N. Karazin Kharkov National University, 4, Svobody Sq., 61077, Kharkov, Ukraine,
⁴A.V. Bogatsky physico-chemical institute of the National Academy of Sciences of Ukraine, 86, Lustdorfskaya doroga, 65080, Odessa, Ukraine

Corresponding author email     

This article is part of the Thematic Series "Multicomponent reactions II".

Guest Editor: T. J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 117–126.

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