The three component reaction involving isocyanides, dimethyl acetylenedicarboxylate and...

The three component reaction involving isocyanides,dimethyl acetylenedicarboxylate and quinoneimides:

a facile synthesis of spirofused g-iminolactams

Vijay Nair,* R. Dhanya and S. Viji

Organic Chemistry Division, Regional Research Laboratory, Trivandrum 695 019, Kerala, India

Received 7 February 2005; revised 21 March 2005; accepted 7 April 2005

Available online 10 May 2005

Abstract—The three component reaction of the zwitterion generated from dimethyl acetylenedicarboxylate and isocyanides with variousquinoneimides is described. The reaction afforded the corresponding g-spiroiminolactams in good yields.q 2005 Elsevier Ltd. All rights reserved.

1. Introduction

Quinonoid compounds have assumed great importance,since they find application as pharmaceuticals, hormones,and pigments besides playing very crucial roles inphotosynthesis and electron transport chains in a numberof biological processes. They are also versatile buildingblocks in organic synthesis by virtue of their multiplereactivity profiles.1 Our own studies have uncovered somenovel reaction pathways of o-quinones, especially in thearea of cycloadditions.2 In contrast, however, the reactivityof quinoneimides,3 the aza analogs of quinones, hasreceived much less attention.4 The available reports on thechemistry of p-quinoneimides are essentially focussed onthe addition of weak nucleophiles,5 whereas the chemistryof o-quinoneimides has been mainly concerned with theirparticipation in Diels–Alder reaction with alkenes andfulvenes.6 Very recently, Parker and Mindt have reportedthe formation of quinolines and indoles from enolalizablep-quinoneimides.7

As a part of our ongoing project in the area of cycloadditionreactions of quinoneimides8 as well as the chemistry ofzwitterions, generated by the addition of various nucleo-philic species to dimethyl acetylenedicarboxylate(DMAD),9 we undertook a detailed investigation of thereactivity of zwitterion generated from the latter and alkylisocyanides to various quinoneimides. Expect for the twoexamples on the addition of this zwitterionic species to

0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.doi:10.1016/j.tet.2005.04.008

Keywords: Multicomponent reactions; Isocyanide; Quinoneimide; Lactam;Dimethyl acetylenedicarboxylate.* Corresponding author. Tel.: C91 471 2490406; fax: C91 471 2491712;

e-mail: [email protected]

p-quinonediimides reported by us,10 there has been nosystematic investigation in this area. In particular there areno reports on their addition to p-quinonemonoimides ando-quinonediimides. For our present studies p-quinonedi-imides, p-quinonemonoimides and o-quinonediimides wereused as the electrophiles for trapping the zwitterion. Theresults of the investigations carried out on such systems arepresented in this paper.

2. Results and discussion

2.1. Reaction with p-quinonediimides

In an initial experiment, we treated the p-quinonediimide 1aand DMAD 2a with stoichiometric amount of cyclohexylisocyanide 3a in refluxing benzene under an atmosphere ofargon for 4 h. A facile reaction occurred and the reactionmixture on silica gel column chromatography afforded theg-iminolactam 4a as a pale yellow crystalline solid in 64%yield (Scheme 1).

The product 4a was characterized on the basis of spectro-scopic data. The IR spectrum showed strong absorption due

Tetrahedron 61 (2005) 5843–5848

Scheme 1.

V. Nair et al. / Tetrahedron 61 (2005) 5843–58485844

to ester carbonyl at 1744 cmK1 and the carbonyl absorptionof the benzoyl group was seen at 1667 cmK1. Thecharacteristic bands due to sulfonyl absorption were seenat 1331 and 1175 cmK1. In the 1H NMR spectrum, the twocarbomethoxy groups were discernible as singlets at d 3.86and 3.75. The tertiary cyclohexyl proton displayed amultiplet at d 3.17; other protons were discernible asmultiplets between d 1.72 and 1.11. The four olefinicprotons on the cyclohexadiene ring resonated as twoseparate doublets, one centered at d 6.63 (JZ9.7 Hz, 2H)and the other centered at d 6.46 (JZ9.7 Hz, 2H). In the 13CNMR spectrum, the peak at d 179.9 was assigned to thecarbonyl resonance due to the benzimide functionality. Theester carbonyls were visible at d 163.8. The resonance due tothe imino carbon was observed at d 155.2. The spirocarbonsignal appeared at d 66.7 and the methoxy carbons wereobserved at d 53.2 and 53.0. The signal at d 59.5 wasattributed to the carbon atom on the cyclohexyl ringadjacent to the nitrogen. All other signals were also ingood agreement with the proposed structure.

The following rationalization may be invoked for theformation of the product. Conceivably the starting point ofthe reaction is the formation of a 1:1 zwitterionic species Abetween cyclohexyl isocyanide and DMAD, which adds tothe quinonediimide, in a chemoselective manner to theC]N of the sulfonimide leading to the dipolar intermediateB. Cyclization of the latter then completes the reactionsequence leading to the iminolactam 4a. Although lesslikely, an alternate mechanism involving the 1,3-dipolarcycloaddition reaction of the zwitterionic intermediate A, tothe C]N bond of the quinoneimide as shown in Scheme 2,cannot be excluded.

Scheme 2.

Table 1. Reaction of p-quinoediimides and acetylenes with isocyanides

Entry Quinonemonoimides Acet

1 R1ZSO2Ph, R2ZCOPh, R3ZR4ZH, 1a EZC2 R1ZR2ZSO2Ph, R3ZR4ZCH3, 1b EZC3 R1ZR2ZSO2Ph, R3ZR4ZCH3, 1b EZC4 R1ZR2ZTs, R3ZR4ZH, 1c EZC5 R1ZR2ZTs, R3ZCl, R4ZH, 1d EZC6 R1ZR2ZCOPh, R3ZR4ZH, 1e EZC

Similar reactivity was observed with other p-quinonedi-imides, which underwent a facile reaction with thezwitterions formed from DMAD and isocyanides to affordthe corresponding iminolactam derivatives. The resultsobtained are summarized in Table 1.

From Table 1, it is clear that the reaction is general withrespect to quinoneimide and isocyanide components. In allthe cases, products were isolated by column chromato-graphy and were characterized on the basis of spectroscopicdata. The regiochemistry of the product 4f was establishedby comparing its 13C NMR data with those of the startingquinoneimide 1d. Attempts were made to intercept both theimide functionalities of the p-quinoneimides, but the resultswere not promising.

2.2. Reaction with p-quinonemonoimides

p-Quinonemonoimides offer multiple electrophilic sites,11

and therefore it was of interest to examine the reactivityprofile of the zwitterion towards p-quinonemonoimides.Thus, when 3-methoxy-p-quinonemonobenzenesulfonimide5a was treated with the in situ generated zwitterion, fromDMAD and cyclohexyl isocyanide in refluxing benzene, theiminolactam derivative 6a was obtained in 76% yield.Analogous reactions were observed with other p-quinone-monoimides, DMAD and isocyanides. The results aresummarized in Table 2.

The structure of the adduct 6a, which sheds light on thechemoselectivity of the reaction, was established byspectroscopic methods. In the IR spectrum, the charac-teristic dienone carbonyl absorption was observed at1662 cmK1. In the 13C NMR spectrum, the characteristicresonance signal due to the dienone carbonyl appeared atd 188.4. All the other peaks were in agreement with theproposed structure.

2.3. Reaction with o-quinonediimides

In view of the results obtained by the addition of thezwitterionic intermediate generated from DMAD andisocyanides to both p-quinonemono- and di-imides, alogical extension of the work was to explore the reactivityof o-quinonediimides towards the zwitterionic intermediate.o-Quinonediimides can, in principle, exhibit four differentreactivity modes. But in the studies carried out so far, they

ylene Isocyanide Time (h) Product (%)

O2Me tBuNC 4 4b (69)OPh CyNC 12 4c (61)O2Me tBuNC 6 4d (82)O2Me tBuNC 6 4e (62)O2Me tBuNC 6 4f (62)O2Me CyNC 6 4g (57)

Table 2. Reaction of p-quinonemonoimides and acetylenes with isocyanides

Entry p-Quinonemonoimides Acetylene Isocyanide Product (%)

1 R1ZOMe, R2ZH, 5a EZCO2Me CyNC 6a (64)2 R1ZH, R2ZOMe, 5b EZCO2Me CyNC 6b (69)3 R1ZH, R2ZOMe, 5b EZCO2Me tBuNC 6c (72)4 R1ZR2ZH, 5c EZCO2Me CyNC 6d (66)5 R1ZOMe, R2ZH, 5b EZCOPh tBuNC 6e (56)

(i) Benzene, 80 8C, Ar, 6 h

Table 3. Reaction of o-quinonediimides and DMAD with isocyanides

Entry o-Quinonemonoimides Isocyanide Product (%)

1 R1ZR2ZMe, R3ZSO2Ph, 7a tBuNC 8a (64)2 R1ZR2ZMe, R3ZSO2Ph, 7a CyNC 8b (48)3 R1ZR2ZH, R3ZCOPh, 7b CyNC 8c (52)4 R1ZR2ZMe, R3ZCOPh, 7c CyNC 8d (53)

V. Nair et al. / Tetrahedron 61 (2005) 5843–5848 5845

have manifested only two different reactivity modes viz. ascarbodiene or as heterodiene.4a In a pilot experiment, weobserved that a mixture of 4,5-dimethyl-o-benzoquinonedi-sulfonimide 7a, and DMAD at 80 8C, when treated withcyclohexyl isocyanide afforded the iminolactam derivative8a in 64% yield. As usual, the product was separated bysilica gel column chromatography and characterized on thebasis of spectroscopic methods. Analogous reactions wereobserved with other substituted o-quinonediimides and theresults are presented in Table 3.

In the IR spectrum of 8a, the absorption band due to theester carbonyls was seen at 1727 cmK1. The peaks at 1336and 1161 cmK1 were attributed to sulfonyl absorptions. Inthe 1H NMR spectrum of 8a, protons of the tert-butyl groupexhibited a sharp singlet at d 1.29. The two methyl groupson the cyclohexadiene ring were observed as two separatesinglets at d 2.01 and 1.46, while the two carbomethoxygroups were observed at d 3.95 and 3.47. The two protons ofthe cyclohexadiene ring gave two singlets at d 7.43 and 5.85.In 13C the NMR spectrum, the carbomethoxy carbonylresonances were discernible at d 173.3 and 168.5. The peakat d 61.2 was attributed to the spiro carbon. The signal due tothe methyl carbons of the tert-butyl group was seen at d30.1. All the other peaks were in good agreement with theassigned structure.

3. Conclusion

In summary, our studies have shown that the interception ofthe zwitterionic intermediate, generated by the addition of

isocyanides to DMAD, using quinoneimides offers aconvenient method for the synthesis of spiroiminolactams.The presence of transformable functionalities in theseproducts makes them potentially valuable from the vantagepoint of further synthetic manipulations.

4. Experimental

4.1. General

All reactions were carried out in oven-dried glasswaresunder an atmosphere of argon. Progress of reaction wasmonitored by thin layer chromatography, while purificationwas effected using silica gel column chromatography. NMRspectra were recorded at 300 (1H) and 75 (13C) MHz,respectively, on a Brucker DPX-300 MHz spectrometer.Chemical shifts (d) were reported relative to TMS (1H) andCDCl3 (13C) as the internal standards. Coupling constant (J)is reported in Hertz (Hz). IR spectra were recorded inBomem MB Series FT-IR spectrophotometer. Meltingpoints were recorded on a Buchi melting point apparatusand are uncorrected. All the quinoneimides were preparedaccording to the literature procedure.12–14Commercial gradesolvents were distilled prior to use.

4.1.1. Dimethyl 2-(cyclohexylimino)-1-(phenylsulfonyl)-8-[(benzoyl)imino]-1-azaspiro[4.5]deca-3,6,9-triene-3,4-dicarboxylate 4a: Typical procedure and spectral data.A mixture of p-quinoneimide 1a (70 mg, 0.2 mmol) andDMAD (32 mg, 0.22 mmol) in dry benzene (4 mL) waspurged with argon. To this mixture, cyclohexyl isocyanide


(24 mg, 0.22 mmol) was added and the refluxing wascontinued at 80 8C for 4 h. The solvent was removed undervacuum and the residue was purified by chromatography onsilica gel using 80:20 hexane/ethylacetate as eluent gave theiminolactam 4a as a pale yellow crystalline solid (77 mg,64%). The products were recrystallized from dichloro-methane–hexane solvent system.

Pale yellow crystalline solid, mp: 158–159 8C, IR (KBr)nmax: 2934, 2856, 1744, 1667, 1600, 1450, 1331, 1268,1175, 1087, 1020, 731 cmK1. 1H NMR: d 1.11–1.72 (m,10H), 3.17 (m, 1H), 3.75 (s, 3H), 3.86 (s, 3H), 6.46 (d, 2H,JZ9.7 Hz), 6.63 (d, 2H, JZ9.7 Hz), 7.44–7.49 (m, 4H),7.57–7.58 (m, 2H), 7.99–8.03 (m, 4H). 13C NMR: d 24.5,25.4, 29.7, 34.6, 53.0, 53.2, 59.5, 66.7, 127.4, 128.0, 128.1,128.6, 129.5, 129.7, 131.6, 132.0, 133.0, 133.3, 133.4,134.0, 138.6, 139.2, 143.0, 143.6, 155.2, 163.8, 179.9.

HRMS (EI) calcd for C31H31N3O7S: 601.1883. Found:601.1869.

4.1.2. Dimethyl 2-(tert-butylimino)-1-(phenylsulfonyl)-8-[(benzoyl)imino]-1-azaspiro[4.5]deca-3,6,9-triene-3,4-dicarboxylate 4b. Pale yellow crystalline solid, mp: 144–146 8C, IR (KBr) nmax: 2960, 2365, 1739, 1677, 1600, 1450,1315, 1268, 1087, 1015, 803 cmK1. 1H NMR: d 1.11 (s,9H), 3.72 (s, 3H), 3.82 (s, 3H), 6.55 (d, 2H, JZ9.7 Hz), 6.64(d, 2H, JZ9.7 Hz), 7.23–7.50 (m, 4H), 7.54–7.58 (m, 2H),7.93–8.00 (m, 4H). 13C NMR: d 31.0, 52.9, 53.1, 56.1, 64.9,127.3, 127.4, 128.2, 128.6, 128.8, 128.9, 129.7, 131.6,133.0, 133.1, 133.2, 133.3, 134.9, 140.0, 140.1, 143.4,155.3, 163.8, 179.9.


4.1.3. 3,4-Bisbenzoyl-2-(cyclohexylimino)-1-(phenyl-sulfonyl)-8-[(phenylsulfonyl)imino]-1-azaspiro[4.5]deca-3,6,9-triene 4c. Pale yellow crystalline solid; mp: 112–114 8C, IR (KBr) nmax: 2924, 2851, 1667, 1543, 1450, 1336,1258, 1165, 1093, 752, 725, 689 cmK1. 1H NMR: d 1.32–1.16 (m, 10H), 1.82 (s, 3H), 2.28 (s, 3H), 2.97 (m, 1H), 6.64(s, 1H), 6.77 (s, 1H), 7.55–7.31 (m, 12H), 7.62 (d, 4H, JZ8.0 Hz), 8.05 (d, 2H, JZ8.9 Hz), 8.11 (d, 2H, JZ8.0 Hz).13C NMR: d 17.0, 19.6, 24.3, 25.3, 29.8, 34.5, 60.9, 71.2,123.2, 127.1, 128.1, 128.5, 128.7, 128.9, 129.1, 129.3,129.7, 129.8, 129.9, 132.4, 133.7, 134.3, 134.9, 137.6,139.2, 139.5, 145.9, 154.5, 164.1, 189.7.

Mass spectrometric analysis (FAB) calcd forC43H39N3O6S2CH: 758.23. Found: 758.24.

4.1.4. Dimethyl 2-(tert-butyllimino)-6,9-dimethyl-1-(phenylsulfonyl)-8-[(phenylsulfonyl)imino]-1-azaspiro-[4.5]deca-3,6,9-triene-3,4-dicarboxylate 4d. Pale yellowcrystalline solid, mp: 85–88 8C, IR (KBr) nmax: 2960, 2365,1739, 1677, 1600, 1450, 1315, 1268, 1087, 1015, 803 cmK1.1H NMR: d 1.20 (s, 9H), 1.87 (s, 3H), 2.08 (s, 3H), 3.68 (s,3H), 3.82 (s, 3H), 6.41 (s, 1H), 7.40–7.61 (m, 7H), 7.96–8.12 (m, 4H). 13C NMR: d 17.3, 18.9, 31.2, 53.0, 53.1, 56.2,67.7, 123.7, 127.0, 128.1, 128.8, 129.2, 132.5, 133.3, 138.0,138.4, 139.3, 139.4, 139.7, 142.0, 153.8, 163.6, 165.4.

Anal. Calcd for C31H33N3O8S2: C, 58.20; H, 5.20; N, 6.57;S, 10.02. Found: C, 58.01; H, 5.62; N, 6.61; S, 9.73.

4.1.5. Dimethyl 2-(tert-butylimino)-1-[(4-methylphenyl)sulfonyl]-8-{[(4-methylphenyl)sulfonyl]imino}-1-aza-spiro[4.5]deca-3,6,9-triene-3,4- dicarboxylate 4e. Paleyellow crystalline solid, mp: 170–172 8C, IR (KBr) nmax:2975, 1739, 1667, 1548, 1315, 1274, 1170, 1082, 1015, 870,770, 668 cmK1. 1H NMR: d 1.12 (s, 9H), 2.45 (s, 6H), 3.63(s, 3H), 3.75 (s, 3H), 6.54 (d, 1H, JZ8.1 Hz), 6.74 (d, 2H,JZ8.3 Hz), 7.26–7.29 (m, 4H), 7.34 (d, 1H, JZ8.1 Hz),7.81–7.90 (m, 4H). 13C NMR: d 21.6, 21.7, 31.1, 53.1, 53.2,56.2, 64.9, 125.0, 127.4, 128.9, 129.2, 129.5, 131.3, 136.2,138.2, 138.6, 136.8, 141.7, 142.5, 143.7, 144.2, 163.4,163.7.

Anal. Calcd for C31H33N3O8S2: C, 58.20; H, 5.20; N, 6.57;S, 10.02. Found: C, 58.07; H, 5.57; N, 6.63; S, 9.7.

4.1.6. Dimethyl 2-(tert-butylimino)-7-chloro-1-[(4-methylphenyl)sulfonyl]-8-{[(4-methylphenyl)sulfonyl]-imino}-1-azaspiro[4.5]deca-3,6,9-triene-3,4-dicarboxylae4f. Pale yellow crystalline solid; mp: 140–142 8C, IR (KBr)nmax: 2924, 1734, 1672, 1563, 1439, 1320, 1279, 1160,1082, 1025, 870, 808 cmK1. 1H NMR: d 1.19 (s, 9H), 2.40(s, 3H), 2.45 (s, 3H), 3.72 (s, 3H), 3.83 (s, 3H), 6.73 (d, 2H,JZ9.9 Hz), 7.26–7.35 (m, 4H), 7.81–7.87 (m, 4H), 6.85(s, 1H). 13C NMR: d 21.6, 21.7, 31.2, 53.0, 53.2, 56.4, 65.6,124.3, 124.4, 127.3, 127.4, 128.7, 128.9, 129.2, 129.4,129.5, 129.9, 131.0, 136.5, 139.4, 141.3, 142.5, 142.8,143.8,144.5, 162.5, 184.2.

HRMS (EI) calcd for C31H32ClN3O8S2: 673.1319. Found:673.1320.

4.1.7. Dimethyl 2-(cyclohexylimono)-1-(benzoyl)-8-[(benzoyl)imino]-1-azaspiro-[4.5]deca-3,6,9-triene-3,4-dicarboxylate 4g. Pale yellow semi solid, IR (neat) nmax:2934, 2856, 1744, 1667, 1600, 1450, 1331, 1268, 1175,1087, 1020, 731 cmK1. 1H NMR: d 1.26–1.63 (m, 10H),3.25 (m, 1H), 3.76 (s, 3H), 3.83 (s, 3H), 6.52 (d, 2H, JZ9.8 Hz), 6.66 (d, 2H, JZ9.8 Hz), 7.16–7.66 (m, 10H). 13CNMR: d 24.5, 26.6, 29.3, 37.8, 52.7, 53.1, 59.6, 65.8, 120.4,125.2, 126.9, 127.4, 127.8, 128.2, 128.4, 128.6, 128.8,129.2, 129.3, 130.0, 130.3, 130.5, 131.3, 134.4, 144.3,162.3, 164.9, 167.9, 176.7.

HRMS (EI) calcd for C33H31N3O6: 565.2213. Found:565.2208.

4.1.8. Dimethyl 2-(cyclohexylimino)-6-methoxy-8-oxo-1-(phenylsulfonyl)-1-azaspiro[4.5]deca-3,6,9-triene-3,4-dicarboxylate 6a. Pale yellow crystalline solid, mp: 186–188 8C, IR (KBr) nmax: 2918, 2846, 1732, 1662, 1605, 1444,1408, 1382, 1222, 1087 cmK1. 1H NMR: d 1.73–1.17 (m,10H), 3.16–3.23 (m, 1H), 3.43 (s, 3H), 3.63 (s, 3H), 3.74 (s,3H), 5.78 (s, 1H), 6.41 (d, 1H, JZ9.8 Hz), 6.49 (d, 1H, JZ9.8 Hz), 7.44–7.49 (m, 2H), 7.56–7.61 (m, 1H), 8.00 (d, 2H,JZ7.8 Hz). 13C NMR: d 19.8, 24.4, 32.9, 34.6, 52.8, 53.1,56.2, 59.4, 67.0, 104.6, 116.9, 126.0, 127.9, 129.3, 131.1,133.3, 134.6, 138.9, 139.2, 139.3, 143.9, 152.9, 163.5,168.2, 188.4.

V. Nair et al. / Tetrahedron 61 (2005) 5843–5848 5847


4.1.9. Dimethyl 2-(cyclohexylimino)-7-methoxy-8-oxo-1-(phenylsulfonyl)-1-azaspiro[4.5]deca-3,6,9-triene-3,4-dicarboxylate 6b. Pale yellow crystalline solid, mp: 138–140 8C, IR (KBr) nmax: 2929, 2851, 1765, 1734, 1662, 1605,1548, 1439, 1356, 1294, 1232, 1155, 1087, 1020, 989,793 cmK1. 1H NMR: d 1.19–1.73(m, 10H), 3.41–3.54 (m,1H), 3.67 (s, 3H), 3.78 (s, 3H), 3.93 (s, 3H), 5.67 (s, 1H),6.29 (d, 1H, JZ9.7 Hz), 6.38 (d, 1H, JZ9.7 Hz), 7.54–7.71(m, 3H), 8.00 (d, 2H, JZ7.1 Hz). 13C NMR: d 24.7, 25.7,29.6, 33.3, 52.9, 53.2, 56.4, 57.1, 97.7, 103.5, 127.2, 128.8,130.8, 131.7, 132.7, 136.9, 137.8, 153.6, 165.6, 167.7,185.9.


4.1.10. Dimethyl 2-(tert-butylimino)-7-methoxy-8-oxo-1-(phenylsulfonyl)-1-azaspiro[4.5]deca-3,6,9-triene-3,4-dicarboxylate 6c. Pale yellow crystalline solid; mp: 176–178 8C, IR (KBr) nmax: 2970, 1775, 1739, 1662, 1548, 1439,1356, 1222, 1165, 1031, 984, 798 cmK1. 1H NMR: d1.27 (s,9H), 3.72 (s, 3H), 3.79 (s, 3H), 3.91 (s, 3H), 5.65 (s, 1H),6.61 (d, 1H, JZ8.6 Hz), 6.79 (d, 1H, JZ8.6 Hz), 7.54–7.60(m, 3H), 7.99 (d, 2H, JZ8.2 Hz). 13C NMR: d 29.9, 52.5,52.8, 56.2, 56.8, 82.7, 103.2, 126.9, 128.4, 128.6, 128.7,130.5, 131.4, 132.5, 136.9, 137.7, 139.4, 140.7, 159.5,165.4, 167.5, 185.6.


4.1.11. Dimethyl 2-(cyclohexylimino)-8-oxo-1-(phenyl-sulfonyl)-1-azaspiro[4.5]deca-3,6,9-triene-3,4-dicarb-oxylate 6d. Pale yellow semi solid, IR (neat) nmax: 2924,1763, 1734, 1672, 1563, 1439, 1350, 1289, 1160, 1082,1025, 870, 808 cmK1. 1H NMR: d 1.26–1.77 (m, 10H), 3.13(m, 1H), 3.87 (s, 3H), 3.93 (s, 3H), 6.65 (d, 2H, JZ7.9 Hz),6.86 (d, 2H, JZ7.9 Hz), 7.91 (d, 2H, JZ6.9 Hz), 7.67–7.56(m, 3H). 13C NMR: d 24.5, 25.5, 29.7, 33.8, 51.9, 52.1, 59.6,99.2, 115.9, 125.8, 126.4, 127.3, 128.8, 129.0, 132.5, 132.6,133.8, 144.7, 159.1, 161.5, 165.0, 179.5.


4.1.12. 3,4-Bisbenzoyl 2-(tert-butyliminoimino)-7-meth-oxy-8-oxo-1-(phenylsulfonyl)-1-azaspiro[4.5]deca-3,6,9-triene 6e. Pale yellow crystalline solid, mp: 126–128 8C, IR(KBr) nmax: 2924, 1758, 1734, 1672, 1563, 1439, 1320,1279, 1160, 1082, 1025, 870, 808 cmK1. 1H NMR: d 1.28 (s,9H), 3.98 (s, 3H), 5.74 (s, 1H), 6.35 (d, 1H, JZ8.4 Hz), 6.51(d, 1H, JZ8.4 Hz), 7.34–7.29 (m, 4H), 7.51–7.62 (m, 7H),7.99 (d, 4H, JZ6.8 Hz). 13C NMR: d 29.7, 55.4, 57.0, 83.8,111.4, 127.2, 127.5, 128.5, 128.6, 128.7, 128.8, 129.3,129.4, 131.5, 132.7, 134.1, 134.3, 135.8, 136.1, 137.3,148.0, 165.4, 168.2, 188.6, 189.1.

HRMS (EI) calcd for C34H30N2O6S: 594.1825. Found: 594.1823.

4.1.13. Dimethyl 2-(tert-butylimino)-7,8-dimethyl-1-(phenylsulfonyl)-10-[(phenylsulfonyl)imino]-1-azaspiro-[4.5]deca-3,6,8-triene-3,4-dicarboxylate 8a. Pale yellowcrystalline solid, mp: 144–145 8C, IR (KBr) nmax: 2969,1727, 1660, 1516, 1449, 1336, 1269, 1161, 1094, 1017, 908,687 cmK1. 1H NMR: d1.29 (s, 9H), 1.46 (s, 3H), 2.01 (s,3H), 3.47 (s, 3H), 3.95 (s, 3H), 5.85 (s, 1H), 7.43 (s, 1H),7.46–7.52 (m, 6H), 7.57 (d, 2H, JZ8.3 Hz), 8.05 (d, 2H,JZ7.4 Hz). 13C NMR: d 18.5, 20.0, 30.1, 51.6, 53.6, 61.2,62.7, 111.6, 114.0, 118.0, 121.0, 127.1, 127.5, 127.8, 128.2,128.4, 128.6, 128.7, 128.8, 128.9, 129.9, 132.6, 132.7,133.1, 136.9, 138.5, 138.8, 139.9, 168.5, 173.3.


4.1.14. Dimethyl 2-(cyclohexylimino)-7,8-dimethyl-1-(phenylsulfonyl)-10-[(phenylsulfonyl)imino]-1-azaspiro-[4.5]deca-3,6,8-triene-3,4-dicarboxylate 8b. Pale yellowcrystalline solid; mp: 148–150 8C, IR (KBr) nmax: 2929,2846, 1729, 1667, 1600, 1450, 1331, 1268, 1175, 1087,1020, 731 cmK1. 1H NMR: d 1.71–1.22 (m, 10H), 2.03 (s,3H), 2.17 (m, 1H), 2.21 (s, 3H), 3.67 (s, 3H), 4.07 (s, 3H),4.89 (s, 1H), 6.50 (s, 1H), 7.31–7.79 (m,10H). 13C NMR: d18.9, 20.1, 24.8, 25.5, 32.8, 51.6, 53.7, 59.6, 72.9, 111.6,120.8, 127.2, 127.5, 128.5, 128.9, 129.2, 131.3, 132.5,132.6, 133.0, 133.5, 134.3, 140.2, 145.7, 163.5.


4.1.15. Dimethyl 2-(cyclohexylimino)-1-benzoyl-10-[(benzoyl)imino]-1-azaspiro[4.5] deca-3,6,8-triene-3,4-dicarboxylate 8c. Pale yellow crystalline solid, mp: 120–122 8C, IR (KBr) nmax: 2928, 1737, 1676, 1563, 1439, 1279,1160, 1082, 1025, 870, 808 cmK1. 1H NMR: d 0.98–1.67(m, 10H), 2.02 (m, 1H), 3.65 (s, 3H), 3.98 (s, 3H), 6.95 (d,1H, JZ7.3 Hz), 7.30–7.38 (m, 6H), 7.39–7.57 (m, 4H), 8.04(d, 2H, JZ7.7 Hz), 8.71 (d, 2H, JZ8.4 Hz). 13C NMR: d23.8, 29.7, 32.9, 51.9, 53.2, 62.1, 70.1, 113.7, 124.4, 127.5,127.7, 127.9, 128.3, 128.4, 128.7, 129.2, 129.9, 130.3,131.8, 132.2, 132.9, 134.3, 145.6, 164.7, 166.8.

Mass spectrometric analysis (FAB) calcd for C33H31N3O6

CH: 567.22. Found: 567.86.

4.1.16. Dimethyl 2-(cyclohexylimino)-1-benzoyl-10-[(benzoyl)imino]-7,8-dimethyl-1-azaspiro[4.5]deca-3,6,8-triene-3,4-dicarboxylate 8d. Pale yellow crystallinesolid, mp: 88–90 8C, IR (KBr) nmax: 2924, 2866, 1746,1674, 1605, 1528, 1445, 1255, 1014, 776 cmK1. 1H NMR:d1.26–1.76 (m, 10H), 2.15 (s, 3H), 2.35 (s, 3H), 2.37 (m,1H), 3.72 (s, 3H), 3.83 (s, 3H), 6.37 (s, 1H), 7.13 (s, 1H),7.54–7.31(m, 4H), 7.98–7.74 (m, 4H), 8.34 (d, 2H, JZ8.8 Hz). 13C NMR: d 15.9, 16.6, 26.4, 29.6, 30.7, 51.9, 53.0,63.2, 122.3, 126.3, 127.0, 127.4, 127.9, 128.2, 128.3, 128.4,128.5, 128.8, 129.9, 130.1, 131.8, 132.1, 133.0, 139.0,156.3, 165.1, 169.6, 174.4.

Mass spectrometric analysis (FAB) calcd forC35H35N3O6CH: 594.25. Found: 594.43.


Acknowledgements

R. D. thanks the CSIR, New Delhi for a research fellowship.

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