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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See Translation

 



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Zanthodione

.


Spectroscopic data
Zanthodione (I): orange needles; mp. 254-256 °C; 

UV (MeOH) λ_max (log E) 239 (sh) (4.49), 249 (4.51), 392 (sh) (3.58), 408 (4.51), 428 (3.58) ñm; 

IR (KBr) v_max 3389 (OH); 1660, 1646 (C=0); 1601, 1460 (aromatic ring C=C); 1040, 94°6^X(OCH₂0) cm^-1; 

¹H NMR (CDC1₃, 600 MHz) δ 6.40 (2H, s, OCH₂0), 7.73 (1H, br ddd, J = 8.4, 7.2, 1.8 Hz, H-10), 7.77 (1H, dt, J = 7.2, 1.2 Hz, H-9), 8.04 (1H, s, H-7), 8.26 (1H, s, NH exchangeable with D₂0), 8.29 (1H, dd, J = 7.2, 1.8 Hz, H-8), 9.26 (1H, d, J = 8.4 Hz, H-ll), 11.98 (1H, s, OH exchangeable with D₂0); 

EIMS m/z 307 [M]⁺ (90); 

HRESIMS m/z 307.1481 (caled for C₁₇H₉NO_s, 307.1480).




Zanthodione (I) was obtained as orange needles. Its molecular formula C₁₇H₉NO_s was established by EIMS ([M]⁺, m/z 307) and HRESIMS. The UV spectrum showed absorption máxima at 239 (sh), 240, 249, 392 (sh), 408, 428 nm, that indicated the presence of a 4,5-dioxoaporphine skeleton.^11,12 Its IR spectrum indicated the presence of OH/NH (3000—3389 cm^-1), two aryl ketone C=0 (1660, 1646 cm^-1), one methylenedioxy (1040, 940 cm¹) and a six-membered lactam (1587 cm^-1) functionalities. The ¹H NMR spectrum revealed five aromatic protons, two D₂0 exchangeable singlets of a H-bonded phenolic hydroxyl [8 11.98 (1H, s)], and an amidocarbonyl proton at 8 8.26 (1H, s), and a methylenedioxy group at 8 6.40 (2H, s). Five aromatic protons of the spectrum closely resembled those of other 7,8,9,10,11-unsubstituted dioxoaporphine.^11,12 Therefore, the methylenedioxy group had to be on ring A. The singlet at δ 8.04 (1H, s) was ascribed to H-7 while H-8, H-9, H-10 and H-ll appeared as a complex ABCX coupling system. In agreement with the spectra of other C-11-unsubstituted aporphines, dehydro- and oxoaporphines, the most downfield doublet [δ 9.26 (1H, s)] was characteristic of H-ll, the 2H [δ 7.73 (1H, ddd, J = 8.4, 7.2, 1.8 Hz), 7.77 (1H, dt, J = 7.2, 1.2 Hz)] were assigned to H-10, 9, and another proton at 6 8.29 (1H, dd, J = 7.2, 1.8 Hz) was due to H-8. The correlations of H-7/NH, and H-8/H-7, 9 were also disclosed in the NOESY experiment (Fig. 1) and further supported the position of above assignments. By means of ¹H-NMR, ¹H,¹H-COSY, and NOESY (Fig. 1) data, the structure of zanthodione was shownto be 4-hydroxy-7H-benzo[g][l,3]dioxolo[4',5';4,5 ]benzo[l,2,3-úfe]quinoline-5,6-dione (1).

 see...................
 http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072008000300019&lng=en&nrm=iso&ignore=.html



J. Chil. Chem. Soc, 53, N° 3 (2008) págs: 1631-1634

CHEMICAL CONSTITUENTS FROM THE STEM BARK OF ZANTHOXYLUM SCANDENS

MING-JEN CHENG^1,2,3 CHUAN-FANG LIN^1,3 HSUN-SHUO CHANG¹, IH-SHENG CHEN¹*
¹Graduate Institute of Natural Products , College of Pharmacy, Kaohsiung Medical University, Kaohsiung, Taiwan 807, Republic of China.
²M.-J. C. and C.-F. L. contributed equally to the work in this paper.
Bioresource Collection and Research Center (BCRC), Food Industry Research and Development Institute (FIRDI), Hsinchu, Taiwan 300, Republic of China.

Journal of the Chilean Chemical Society

On-line version ISSN 0717-9707

J. Chil. Chem. Soc. vol.53 no.3 Concepción Sept. 2008

http://dx.doi.org/10.4067/S0717-97072008000300019 

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Hyrtioerectine D, E F

Hyrtioerectine D, E F


Figure 1. Structures of hyrtioerectines D–F (1–3) isolated from the marine sponge Hyrtios species.

Figure 2. COSY and HMBC correlations observed for compound 1.

Structure Elucidation of Compounds 1–3

The HRMS of compound 1 established a molecular formula C₂₀H₁₃N₃O₄ requiring 16 degrees of unsaturation. Compound 1 gave a bluish color on the TLC with FeCl₃ indicating its phenolic nature. Its ¹H NMR spectrum (in methanol-d₄, Table 1) showed resonances for eight aromatic protons ranging from 6.80 to 9.64 ppm, suggesting the absence of any aliphatic moiety in the molecule. The ¹³C NMR spectrum of 1 (Table 1) displayed resonances for 20 carbons including 8 methines and 12 quaternary carbons. Two of the ¹³C quaternary resonances were deshielded at δ 154.3 (C-6) and 153.0 (C-6′) suggesting the oxygenation of their corresponding carbons. Interpretation of the 1D (¹H and ¹³C) and 2D (¹H–¹H COSY, HSQC and HMBC) NMR spectroscopic data supported the presence of two ABX systems for trisubstituted β-carboline (H-5, H-7 and H-8) and disubstituted indole (H-4ʹ, H-5ʹ and H-7ʹ) moieties, respectively. These two moieties include 15 degrees of unsatuartion suggesting the need for an additional degree of unsaturation in 1. Interpretation of the NMR data (¹H, COSY and HSQC) supported the 3,4,6-trisubstitution of the β-carboline moiety. This was evident from the resonating signals at δ 8.07 (1H, d, J = 2.0, H-5), 6.80 (1H, dd, J = 8.5, 2.0, H-7), 7.30 (1H, d, J = 8.5, H-8) and 9.64 (s, H-1). Additional signals at δ 8.87 (1H, s, H-2ʹ), 7.57 (1H, d, J = 8.7, H-4ʹ), 7.13 (1H, dd, J = 8.7, 2.3, H-5ʹ) and 7.60 (1H, d, J = 2.3, H-7ʹ) were assigned as 3,6-disubstituted indole moiety. The HSQC experiment allowed the unambiguous assignment of the protonated methine carbons in 1 (Table 1). The quaternary carbons were unambiguously assigned from HMBC data (Table 2 and Figure 2). For example, the location of the OH moieties at C-6 and C-6′ was supported from HMBC correlations of H-5/C-6, H-7/C-6, H-8/C-6 and H-4′/C-6′, H-5′/C-6′ and H-7′/C-6′ (Table 2). The connection of the indole and β-carboline moieties through C-3 and C-3ʹ was supported from a ³J_CH HMBC cross peak between H-2ʹ of the indole moiety (δ 8.87) and C-3 of the β-carboline moiety (δ 138.1). Finally, the quaternary carbon resonating at δ 173.0 (C-8′) was assigned as a carboxylic moiety at C-4 completing the degrees of unsaturation in 1. This was supported by an IR band at 1725 cm⁻¹ for the carbonyl moiety of the carboxylic acid. Furthermore, the MS fragment ion at m/z 315.1009 with the molecular formula C₁₉H₁₃N₃O₂ [M − COOH + H]⁺ supported the presence of the carboxylic functionality, thus completing the assignment of 1.
Compound 2displayed a pseudomolecular ion peak at m/z 374.1138 corresponding to C₂₁H₁₆N₃O₄ [M + H]⁺, being 14 mass unit (CH₂) more than 1 and requiring 16 degrees of unsaturation. Comparison of the NMR data of 2 with those of 1 showed identical similarity of the ¹H and ¹³C NMR resonances of both compounds (Table 1). Moreover, a new three-proton singlet in ¹H NMR at δ 3.84 (H₃-9ʹ) correlates in the HSQC with the ¹³C NMR signal at δ 55.8 (C-9ʹ) suggesting the presence of a methoxyl moiety in 2 at C-6. The assignment of the methoxyl moiety at C-6 was secured from HMBC cross peak of OCH₃/C-6 (Table 2). Additionally, the unambiguous assignments of the protonated and quaternary carbons in 2 were secured from HSQC and HMBC experiments, respectively, thus completing the assignment of 2.


Hyrtioerectine D (1): yellow solid; UV (MeOH) λ_max (log ε) 387 nm (3.85), 248 nm (3.85), 312 nm (4.05); IR ν_max (film) 3600, 3500, 3020, 2980, 1725, 1610, 1405, 1290, 1255, 1220, 890 cm⁻¹; NMR data, see Table 1, Table 2; positive HRESIMS m/z 360.0981 (calcd for C₂₀H₁₄N₃O₄ [M + H]⁺, 360.0984).
Hyrtioerectine E (2): yellow solid; UV (MeOH) λ_max (log ε) 420 nm (3.90), 252 nm (3.95), 315 nm (4.15); IR ν_max (film) 3595, 3545, 3015, 2980, 1720, 1612, 1410, 1290, 1250, 1220, 895 cm⁻¹; NMR data, see Table 1, Table 2; positive HRESIMS m/z 374.1138 (calcd for C₂₁H₁₆N₃O₄ [M + H]⁺, 374.1140).
Hyrtioerectine F (3): yellow solid; UV (MeOH) λ_max (log ε) 380 nm (3.95), 240 nm (4.10), 315 nm (4.00); IR ν_max (film) 3590, 3500, 3350, 3010, 2985, 1655, 1615, 1405, 1290, 1255, 1215, 895 cm⁻¹; NMR data, see Table 1, Table 2; positive HRESIMS m/z 359.1142 (calcd for C₂₀H₁₅N₄O₃ [M + H]⁺, 359.1144).

Table 1. NMR spectroscopic data for hyrtioerectines D–F (1–3) (in methanol-d₄).

	Hyrtioerectine D		Hyrtioerectine E		Hyrtioerectine F
Position	δC (mult.) a	δH, mult. (J in Hz)	δC (mult.) a	δH, mult. (J in Hz)	δC (mult.) a	δH, mult. (J in Hz)
1	140.8 (CH)	9.64, s	141.2 (CH)	9.66, s	139.6 (CH)	9.71, s
3	138.1 (qC)		138.2 (qC)		138.3 (qC)
4	138.8 (qC)		138.8 (qC)		138.8 (qC)
4a	115.9 (qC)		115.8 (qC)		115.9 (qC)
4b	130.1 (qC)		130.3 (qC)		130.4 (qC)
5	108.2 (CH)	8.07, d (2.0)	110.1 (CH)	8.10, d (2.2)	107.2 (CH)	8.09, d (2.2)
6	154.3 (qC)		156.2 (qC)		154.2 (qC)
7	113.5 (CH)	6.80, dd (8.5, 2.0)	113.5 (CH)	6.78, dd (8.5, 2.2)	113.7 (CH)	6.76, dd (8.5, 2.2)
8	113.1 (CH)	7.30, d (8.5)	113.1 (CH)	7.27, d (8.5)	113.5 (CH)	7.32, d (8.5)
8a	132.1 (qC)		132.2 (qC)		132.4 (qC)
9a	133.2 (qC)		133.1 (qC)		133.2 (qC)
2′	119.6 (CH)	8.87, s	119.5 (CH)	8.88, s	119.6 (CH)	8.87, s
3′	123.2 (qC)		123.2 (qC)		123.2 (qC)
3a′	137.5 (qC)		137.5 (qC)		137.5 (qC)
4′	114.1 (CH)	7.57, d (8.7)	114.1 (CH)	7.61, d (8.7)	114.1 (CH)	7.64, d (8.0)
5′	119.7 (CH)	7.13, dd (8.7, 2.3)	119.6 (CH)	7.15, dd (8.7, 2.2)	119.7 (CH)	7.17, dd (8.7, 2.0)
6′	153.0 (qC)		153.1 (qC)		153.0 (qC)
7′	106.7 (CH)	7.60, d (2.3)	106.9(CH)	7.62, d (2.2)	106.7 (CH)	7.65, d (2.0)
7a′	132.6 (qC)		132.5 (qC)		132.6 (qC)
8′	173.0 (qC)		173.0 (qC)		164.2 (qC)
9′			55.8 (CH3)	3.84, s

^a multiplicities of the signals were obtained from HSQC experiments; qC = quaternary carbon, CH = methine; CH₃ = methyl.

Table 2. Selected HMBC correlations for hyrtioerectines D–F (1–3) (in methanol-d₄).

C#	Hyrtiooerectine D (1)	Hyrtioerectine E (2)	Hyrtioerectine F (3)
	HMBC (H→C#)	HMBC (H→C#)	HMBC (H→C#)
3	H-1, H-2′	H-1, H-2′	H-1, H-2′
4	-	-	-
4a	H-1, H-5	H-1	H-1, H-5
4b	H-8	H-8	H-8
5	H-7	H-7	H-7
6	H-5, H-7, H-8	H-5, H-7, H-8, H3-9′	H-5, H-8
7	H-5	H-5	H-5
8	H-7	H-7	H-7
8a	H-5, H-7	H-5, H-7	H-5, H-7
9a	H-1	H-1	H-1
2′	-	-	-
3′	H-2′	H-2′	H-2′
3a′	H-2′, H-4′, H-5′, H-7′	H-2′, H-4′, H-7′	H-2′, H-4′, H-7′
4′	H-5′	H-5′	H-5′
5′	H-4′, H-7′	H-4′, H-7′	H-4′, H-7′
6′	H-4′, H-5′, H-7′	H-4′, H-5′, H-7′	H-4′, H-5′, H-7′
7′	H-5′	H-5′	H-5′
7a′	H-2′, H-4′, H-7′	H-2′, H-4′, H-7′	H-2′, H-4′, H-7′

see
 http://www.mdpi.com/1660-3397/11/4/1061/htm

Mar. Drugs 2013, 11(4), 1061-1070; doi:10.3390/md11041061

Article

Bioactive Compounds from the Red Sea Marine Sponge Hyrtios Species

Diaa T. A. Youssef ^1,*, Lamiaa A. Shaala ² and Hani Z. Asfour ³

¹

Department of Natural Products, Faculty of Pharmacy, King Abdulaziz University, Jeddah 21589, Kingdom of Saudi Arabia

²

Natural Products Unit, King Fahd Medical Research Center, King Abdulaziz University, Jeddah 21589, Kingdom of Saudi Arabia

³

Department of Medical Parasitology, Faculty of Medicine, Princess Al-Jawhara Center of Excellence in Research of Hereditary Disorders, King Abdulaziz University, Jeddah 21589, Kingdom of Saudi Arabia

*Author to whom correspondence should be addressed; Tel.: +966-548-535-344; Fax: +966-269-516-96.

 Suez Canal University, Egypt

Suez Canal University  

University in Ismaïlia, Egypt

The Suez Canal University is an Egyptian university serving the Suez Canal area, having its faculties divided among the Suez Canal governorates. It was established in 1964. It is notable for its non-classic research. Wikipedia

Address: EL SALAM DISTRICT، ISMAILEYA، Egypt

 

 

 

 

 
 

 ISMAILEYA، Egypt
 

 

 

 
 

 

 

 
 
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