RSS-Feed abonnieren
Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.
https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000084.xml
Synthesis 2014; 46(10): 1329-1333
DOI: 10.1055/s-0033-1341103
DOI: 10.1055/s-0033-1341103
special topic
Diastereo- and Enantioselective Synthesis of Hexasubstituted Cyclohexanes via a Metal–Organocatalytic Quadruple Cascade Sequence
Weitere Informationen
Publikationsverlauf
Received: 05. Januar 2014
Accepted after revision: 13. März 2014
Publikationsdatum:
27. März 2014 (online)
![](https://www.thieme-connect.de/media/synthesis/201410/lookinside/thumbnails/10.1055-s-0033-1341103-1.jpg)
Abstract
A quadruple cascade reaction, comprising iminium, enamine–copper, iminium, and enamine catalysis, was investigated. This reaction afforded highly optically active hexasubstituted cyclohexanes from α,β-unsaturated aldehydes, nitromethane, and 2,2,6,6-tetramethylpiperidin-1-yloxy (TEMPO). To enhance the stereoselectivity of the organocatalytic cyclization, TEMPO was incorporated into the cyclohexane skeleton using copper catalysts.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis. The copies of 1H NMR, 13C NMR, and HPLC spectra of cyclohexane products are included.
- Supporting Information
-
References and Notes
- 1a Shao Z, Zhang H. Chem. Soc. Rev. 2009; 38: 2745
- 1b Zhou J. Chem. Asian J. 2010; 5: 422
- 1c Zhong C, Shi X. Eur. J. Org. Chem. 2010; 2999
- 2a List B. Chem. Commun. 2006; 819
- 2b Enders D, Grondal C, Hüttl MR. M. Angew. Chem. Int. Ed. 2007; 46: 1570
- 2c Tsogoeva SB. Eur. J. Org. Chem. 2007; 1701
- 2d Yu X, Wang W. Org. Biomol. Chem. 2008; 6: 2037
- 2e Dondoni A, Massi A. Angew. Chem. Int. Ed. 2008; 47: 4638
- 2f Westermann B, Ayaz M, van Berkel SS. Angew. Chem. Int. Ed. 2010; 49: 846
- 2g Pellissier H. Adv. Synth. Catal. 2012; 354: 237
- 2h Wende RC, Schreiner PR. Green Chem. 2012; 14: 1821
- 3a Poe SL, Kobašlija M, McQuade DT. J. Am. Chem. Soc. 2006; 128: 15586
- 3b Poe SL, Kobašlija M, McQuade DT. J. Am. Chem. Soc. 2007; 129: 9216
- 3c Simmons B, Walji AM, MacMillan DW. C. Angew. Chem. Int. Ed. 2009; 48: 4349
- 3d Chercheja S, Nadakudity SK, Eilbracht P. Adv. Synth. Catal. 2010; 352: 637
- 3e Quintard A, Alexakis A. Adv. Synth. Catal. 2010; 352: 1856
- 3f Lin S, Zhao G.-L, Deiana L, Sun J, Zhang Q, Leijonmarck H, Córdova A. Chem. Eur. J. 2010; 16: 13930
- 3g Quintard A, Alexakis A, Mazet C. Angew. Chem. Int. Ed. 2011; 50: 2354
- 3h Rueping M, Sundén H, Hubener L, Sugiono E. Chem. Commun. 2012; 48: 2201
- 3i Du Z, Shao Z. Chem. Soc. Rev. 2013; 42: 1337
- 4a Ibrahem I, Córdova A. Angew. Chem. Int. Ed. 2006; 45: 1952
- 4b Bihelovic F, Matovic R, Vulovic B, Saicic RN. Org. Lett. 2007; 9: 5063
- 4c Ding Q, Wu J. Org. Lett. 2007; 9: 4959
- 4d Binder JT, Crone B, Haug TT, Menz H, Kirsch SF. Org. Lett. 2008; 10: 1025
- 4e Yang T, Ferrali A, Campbell L, Dixon DJ. Chem. Commun. 2008; 2923
- 4f Vulovic B, Bihelovic F, Matovic R, Saicic RN. Tetrahedron 2009; 65: 10485
- 4g Ikeda M, Miyake Y, Nishibayshi Y. Angew. Chem. Int. Ed. 2010; 49: 7289
- 4h Zweifel T, Hollmann D, Prüger B, Nielsen M, Jørgensen KA. Tetrahedron: Asymmetry 2010; 21: 1624
- 5 For selected articles regarding sequential metal/organocatalysis, see refs. 3a–e,g.
- 6a Enders D, Hüttl MR. M, Grondal C, Raabe G. Nature (London) 2006; 441: 861
- 6b Marigo M, Bertelsen S, Landa A, Jørgensen KA. J. Am. Chem. Soc. 2006; 128: 5475
- 6c Carlone A, Marigo M, North C, Landa A, Jørgensen KA. Chem. Commun. 2006; 4928
- 6d Enders D, Hüttl MR. M, Runsink J, Raabe G, Wendt B. Angew. Chem. Int. Ed. 2007; 46: 467
- 6e Carlone A, Cabrera S, Marigo M, Jørgensen KA. Angew. Chem. Int. Ed. 2007; 46: 1101
- 6f Hayashi Y, Okano T, Aratake S, Hazelard D. Angew. Chem. Int. Ed. 2007; 46: 4922
- 6g Reyes E, Jiang H, Milelli A, Elsner P, Hazell RG, Jørgensen KA. Angew. Chem. Int. Ed. 2007; 46: 9202
- 6h Ramachary DB, Reddy YV, Prakash BV. Org. Biomol. Chem. 2008; 6: 719
- 6i Enders D, Jeanty M, Bats JW. Synlett 2009; 3175
- 6j Wang Y, Han R.-G, Zhao Y.-L, Yang S, Xu P.-F, Dixon DJ. Angew. Chem. Int. Ed. 2009; 48: 9834
- 6k Hong B.-C, Nimje RY, Lin C.-W, Liao J.-H. Org. Lett. 2011; 13: 1278
- 6l Ishikawa H, Sawano S, Yasui Y, Shibata Y, Hayashi Y. Angew. Chem. Int. Ed. 2011; 50: 3774
- 6m Mao Z, Jia Y, Xu Z, Wang R. Adv. Synth. Catal. 2012; 354: 1401
- 6n Ma C, Jia Z.-J, Liu J.-X, Zhou Q.-Q, Dong L, Chen Y.-C. Angew. Chem. Int. Ed. 2013; 52: 948
- 6o Zeng X, Ni Q, Raabe G, Enders D. Angew. Chem. Int. Ed. 2013; 52: 2977
- 7a Yoon H.-S, Ho X.-H, Jang J, Lee H.-J, Kim S.-J, Jang H.-Y. Org. Lett. 2012; 14: 3272
- 7b Ho X.-H, Oh H.-J, Jang H.-Y. Eur. J. Org. Chem. 2012; 5655
- 7c Kim J.-H, Park E.-J, Lee H.-J, Ho X.-H, Yoon H.-S, Kim P, Yun H, Jang H.-Y. Eur. J. Org. Chem. 2013; 4337
- 8 CCDC-977839 contains the crystallographic data for 2a; C28H36N2O5, Mr = 480.59, orthorhombic, space group P212121, a = 8.7335(4) Å, b = 15.6355(5) Å, c = 19.6968(6) Å, V = 2689.67(16) Å3, Z = 4, T = 290(1) K, μ(MoKα) = 0.081 mm–1. Of 26365 reflections collected in the θ range 3.0°–27.50° using ω scans on a Rigaku R-axis Rapid S diffractometer, 6162 were unique reflections (R int = 0.0255, completeness = 99.7%). The structure was solved and refined against F 2 using SHELX97, 460 variables, wR 2 = 0.0899, R 1 = 0.0309 [Fo 2 > 2σ(Fo 2)], GOF = 1.107, and max/min residual electron density 0.129/–0.169 e Å–3. Bond lengths and angles are included in the Supporting Information.
For review articles of multi-catalytic reactions using transition-metal catalysts, biocatalysts, and organocatalysts:
For reviews on organocatalytic domino reactions, see ref. 1b and:
For selected recent reviews and articles of tandem organocatalytic reactions using transition-metal complexes, see refs. 1a,c and:
For selected recent articles of transition-metal-catalyzed activation of allyl and alkyne groups for the reaction with enamines, see:
For selected recent articles of organocatalyzed domino reactions for chiral cyclohexane derivatives, see: