Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2013; 24(10): 1197-1200
DOI: 10.1055/s-0033-1338945
DOI: 10.1055/s-0033-1338945
cluster
NHC-Catalyzed Ester Activation: Access to Sterically Congested Spirocyclic Oxindoles via Reaction of α-Aryl Esters and Unsaturated Imines
Further Information
Publication History
Received: 01 April 2013
Accepted after revision: 19 April 2013
Publication Date:
17 May 2013 (online)
![](https://www.thieme-connect.de/media/synlett/201310/lookinside/thumbnails/10.1055-s-0033-1338945-1.jpg)
Abstract
Carboxylic esters can be readily obtained at low cost. Therefore, asymmetric catalytic activation of esters should provide useful strategies for organic synthesis. Here we report a N-heterocyclic carbene (NHC)-mediated reaction of α-aryl acetic esters with oxindole-derived α,β-unsaturated imines. The reaction involves the formation of NHC-bound ester enolate intermediate from an ester as a key step, and furnishes spirocyclic oxindole products. The sterically congested spirocyclic oxindole bears a newly formed six-membered δ-lactams and cannot be easily prepared using other methods.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
- 1a Lin H, Danishefsky SJ. Angew. Chem. Int. Ed. 2003; 42: 36
- 1b Rottmann M, McNamara C, Yeung BK. S, Lee MC. S, Zou B, Russell B, Seitz P, Plouffe DM, Dharia NV, Tan J, Cohen SB, Spencer KR, Gonzalez-Paez GE, Lakshminarayana SB, Goh A, Suwanarusk R, Jegla T, Schmitt EK, Beck HP, Brun R, Nosten F, Renia L, Dartois V, Keller TH, Fidock DA, Winzeler EA, Diagana TT. Science 2010; 329: 1175
- 1c Singh GS, Desta ZY. Chem. Rev. 2012; 112: 6104
- 2a Sebahar PR, Williams RM. J. Am. Chem. Soc. 2000; 122: 5666
- 2b Bencivenni G, Wu L.-Y, Mazzanti A, Giannichi B, Pesciaioli F, Song M.-P, Bartoli G, Melchiorre P. Angew. Chem. Int. Ed. 2009; 48: 7200
- 2c Companyó X, Zea A, Alba A.-NR, Mazzanti A, Moyano A, Rios R. Chem. Commun. 2010; 46: 6953
- 2d Jiang K, Jia Z.-J, Chen S, Wu L, Chen Y.-C. Chem. Eur. J. 2010; 16: 2852
- 2e Jiang K, Jia Z.-J, Yin X, Wu L, Chen Y.-C. Org. Lett. 2010; 12: 2766
- 2f Wang L.-L, Peng L, Bai J.-F, Jia L.-N, Luo X.-Y, Huang Q.-C, Xu X.-Y, Wang L.-X. Chem. Commun. 2011; 47: 5593
- 2g Albertshofer K, Anderson KE, Barbas CF. III. Org. Lett. 2012; 14: 5968
- 2h Bergonzini G, Melchiorre P. Angew. Chem. Int. Ed. 2012; 51: 971
- 3a Chen W.-B, Wu Z.-J, Pei Q.-L, Cun L.-F, Zhang X.-M, Yuan W.-C. Org. Lett. 2010; 12: 3132
- 3b Peng J, Huang X, Jiang L, Cui H.-L, Chen Y.-C. Org. Lett. 2011; 13: 4584
- 3c Albertshofer K, Tan B, Barbas CF. III. Org. Lett. 2012; 14: 1834
- 3d Shen L.-T, Jia W.-Q, Ye S. Angew. Chem. Int. Ed. 2013; 52: 585
- 4a Jiang X, Cao Y, Wang Y, Liu L, Shen F, Wang R. J. Am. Chem. Soc. 2010; 132: 15328
- 4b Wei Q, Gong L.-Z. Org. Lett. 2010; 12: 1008
- 4c Cao Y, Jiang X, Liu L, Shen F, Zhang F, Wang R. Angew. Chem. Int. Ed. 2011; 50: 9124
- 4d Chen W.-B, Wu Z.-J, Hu J, Cun L.-F, Zhang X.-M, Yuan W.-C. Org. Lett. 2011; 13: 2472
- 4e Tan B, Hérnandez-Torres G, Barbas CF. III. J. Am. Chem. Soc. 2011; 133: 12354
- 4f Tan B, Candeias NR, Barbas CF. Nat. Chem. 2011; 3: 473
- 4g Tan B, Zeng X, Leong WW. Y, Shi Z, Barbas CF. III, Zhong G. Chem. Eur. J. 2012; 18: 63
- 4h Cao Y.-M, Shen F.-F, Zhang F.-T, Wang R. Chem. Eur. J. 2013; 19: 1184
- 5a Tan B, Candeias NR, Barbas CF. III. J. Am. Chem. Soc. 2011; 133: 4672
- 5b Zhong F, Han X, Wang Y, Lu Y. Angew. Chem. Int. Ed. 2011; 50: 7837
- 5c Gomez C, Gicquel M, Carry JC, Schio L, Retailleau P, Voituriez A, Marinetti A. J. Org. Chem. 2013; 78: 1488
- 6a Chen X.-H, Wei Q, Luo S.-W, Xiao H, Gong L.-Z. J. Am. Chem. Soc. 2009; 131: 13819
- 6b Cheng M.-N, Wang H, Gong L.-Z. Org. Lett. 2011; 13: 2418
-
7a Enders D, Niemeier O, Henseler A. Chem. Rev. 2007; 107: 5606
-
7b Marion N, Diez-Gonzalez S, Nolan SP. Angew. Chem. Int. Ed. 2007; 46: 2988
- 7c Nair V, Vellalath S, Babu BP. Chem. Soc. Rev. 2008; 37: 2691
- 7d Rovis T. Chem. Lett. 2008; 37: 2
- 7e Glorius F, Hirano K. Ernst Schering Foundation Symposium Proceedings 2008; 2: 159
- 7f Arduengo AJ. III, Iconaru LI. Dalton Trans. 2009; 6903
- 7g Phillips EM, Chan A, Scheidt KA. Aldrichimica Acta 2009; 42: 55
- 7h Moore JL, Rovis T. Top. Curr. Chem. 2011; 291: 77
- 7i Biju AT, Kuhl N, Glorius F. Acc. Chem. Res. 2011; 44: 1182
- 7j Hirano K, Piel I, Glorius F. Chem. Lett. 2011; 40: 786
- 7k Chiang P.-C, Bode JW. TCI MAIL 2011; 149: 2
-
7l Nair V, Menon RS, Biju AT, Sinu CR, Paul RR, Jose A, Sreekumar V. Chem. Soc. Rev. 2011; 40: 5336
- 7m Vora HU, Rovis T. Aldrichimica Acta 2011; 44: 3
- 7n Grossmann A, Enders D. Angew. Chem. Int. Ed. 2012; 51: 314
- 7o Cohen DT, Scheidt KA. Chem. Sci. 2012; 3: 53
- 7p Bugaut X, Glorius F. Chem. Soc. Rev. 2012; 41: 3511
- 8 Nair V, Vellalath S, Poonoth M, Mohan R, Suresh E. Org. Lett. 2006; 8: 507
-
9a Wang X.-N, Zhang Y.-Y, Ye S. Adv. Synth. Catal. 2010; 352: 1892
- 9b Sun L.-H, Shen L.-T, Ye S. Chem. Commun. 2011; 47: 10136
- 9c Zhang B, Feng P, Sun L.-H, Cui Y, Ye S, Jiao N. Chem. Eur. J. 2012; 18: 9198
- 9d Shen LT, Jia WQ, Ye S. Angew. Chem. Int. Ed. 2013; 52: 585
- 10a Jiang K, Tiwari B, Chi YR. Org. Lett. 2012; 14: 2382
- 10b Lv H, Tiwari B, Mo J, Xing C, Chi YR. Org. Lett. 2012; 14: 5412
-
11 Hao L, Du Y, Lv H, Chen X, Jiang H, Shao Y, Chi YR. Org. Lett. 2012; 14: 2154
- 12 General Procedure for the Synthesis of 3 To a 10 mL two-necked oven-dried flask was added ester 1 (0.10 mmol, 2.0 equiv), α,β-unsaturated imine 2 (0.05 mmol) and triazolium salt A (0.015mmol). The flask was then evacuated and refilled with argon. Anhyd (CH2Cl)2 (0.5 mL) was added, followed by an injection of DIPEA (0.25 mmol). The mixture was stirred at r.t. for 24 h. Solvent was removed under reduced pressure, and the residue was purified via column chromatography on silica gel with hexanes–EtOAc as eluent to afford the desired products 3. Compound 3a: yield 78%; 65:35 dr; colorless solid. 1H NMR (400 MHz, CDCl3): δ = 2.47 (s, 3 H), 2.84 (s, 3 H), 4.50 (s, 1 H), 5.83 (s, 1 H), 6.61 (d, 1 H, J = 7.8 Hz), 6.80 (d, 2 H, J = 7.3 Hz), 7.07 (t, 2 H, J = 8.0 Hz), 7.14–7.40 (m, 10 H), 7.88–7.92 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 21.7, 26.0, 53.5, 58.3, 108.2, 119.2, 123.6, 125.1, 126.4, 126.5, 127.6, 128.0, 128.2, 128.6, 129.1, 129.5, 129.8, 130.2, 131.7, 135.9, 136.8, 142.0, 143.3, 145.4, 171.0, 176.0. ESI-HRMS: m/z calcd for [C32H27N2O4S]+: 535.1692; found: 535.1682. HPLC analysis [Chiralcel IA, i-PrOH–hexane (20:80), 0.7 mL/min]: t R (major) = 11.9 min; t R (minor) = 31.2 min; er = 81:19.
For reviews on NHC catalysis, see: