Isocyanide-Based Multicomponent [2+2+1]-Cycloaddition Strategy to 
Construct Functionalized Spirocyclic Oxindoles

Haohua Jie; Jian Li; Chunju Li; Xueshun Jia

doi:10.1055/s-0032-1317030

Synlett, Table of Contents

Synlett 2012; 23(15): 2274-2278
DOI: 10.1055/s-0032-1317030

letter

Isocyanide-Based Multicomponent [2+2+1]-Cycloaddition Strategy to Construct Functionalized Spirocyclic Oxindoles

Authors

Haohua Jie

^aDepartment of Chemistry, Shanghai University, Shanghai, 200444, P. R. of China, Fax: +86(21)66132408 Email: lijian@shu.edu.cn
Jian Li*

^aDepartment of Chemistry, Shanghai University, Shanghai, 200444, P. R. of China, Fax: +86(21)66132408 Email: lijian@shu.edu.cn
Chunju Li

^aDepartment of Chemistry, Shanghai University, Shanghai, 200444, P. R. of China, Fax: +86(21)66132408 Email: lijian@shu.edu.cn
Xueshun Jia*

^aDepartment of Chemistry, Shanghai University, Shanghai, 200444, P. R. of China, Fax: +86(21)66132408 Email: lijian@shu.edu.cn

^bKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China, Email: xsjia@mail.shu.edu.cn

Abstract

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Abstract

Isocyanide-based three-component [2+2+1]-cycloaddition reactions from isocyanides, activated alkynes, and isatylidene malononitriles were investigated to provide a new access to spirocyclic oxindole with five-membered carbon rings. The displacement of isatylidene malononitrile with oxindolylideneacetate essentially results in opposite regioselectivity, which adds to its attractiveness.

Key words

isocyanide - activated alkyne - isatylidene malononitrile - spirocyclic oxindole - oxindolylideneacetate

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References

References and Notes

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14 See the Supporting Information for details
15 CCDC 884218 (4b) and CCDC 884219 (4f) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif
16 CCDC 884217 for compound 7a contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif
17 General Experimental Procedure for 4: Isatylidene malononitrile 3 (0.5 mmol) was added to a solution of isocyanide 1 (0.5 mmol) and alkynoate 2 (0.6 mmol) in toluene (5 mL). The stirred mixture was heated to 100 °C for several hours and the progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was concentrated under vacuum. The residue was purified by column chromatography on silica gel (silica: 200–300; PE–EtOAc) to afford the desired product 4. Compound 4a: Yellow solid; mp 194–196 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.53 (t, J = 7.5 Hz, 1 H), 7.46 (d, J = 7.5 Hz, 1 H), 7.22 (t, J = 7.5 Hz, 1 H), 7.11–7.03 (m, 4 H), 6.86 (s, 1 H), 4.05–3.94 (m, 2 H), 3.37 (s, 3 H), 2.20 (s, 6 H), 1.00 (t, J = 7.0 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 170.6, 161.8, 161.0, 149.7, 146.4, 144.8, 131.7, 131.5, 128.4, 126.6, 125.7, 125.4, 123.9, 123.1, 111.7, 110.6, 109.5, 68.3, 62.5, 62.4, 48.8, 38.9, 18.0, 13.7. HRMS: m/z [M + Na]⁺ calcd for C₂₆H₂₂N₄O₃: 461.1590; found: 461.1595.

Supplementary Material

Supporting Information (PDF)