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-00000083.xml
Synlett 2014; 25(16): 2275-2280
DOI: 10.1055/s-0034-1378564
DOI: 10.1055/s-0034-1378564
cluster
Novel Formal [3+3] Cycloaddition of Silyl Nitronates with Activated Cyclopropanes and Its Application in the Synthesis of Pyrroline-N-oxides
Weitere Informationen
Publikationsverlauf
Received: 12. Mai 2014
Accepted after revision: 14. Juli 2014
Publikationsdatum:
11. August 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201416/lookinside/thumbnails/10.1055-s-0034-1378564-1.jpg)
Abstract
1,1-Cyclopropane diesters with donor substituents undergo formal [3+3] cycloaddition with various silyl nitronates under Yb(OTf)3 catalysis in the presence of a proton scavenger to give target N-silyloxy tetrahydro-1,2-oxazines in 56–98% yield. The reasons determining the reaction diastereoselectivity are discussed. The resulting tetrahydro-1,2-oxazines are transformed into pyrroline-N-oxides via a novel TfOH-promoted silanol elimination reaction.
Key words
formal [3+3] cycloaddition - silyl nitronates - donor–acceptor cyclopropanes - nitrogen heterocycles - ring contractionSupporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
-
References and Notes
-
1a Reissig H.-U, Zimmer R. Chem. Rev. 2003; 103: 1151
- 1b Yu M, Pagenkopf BL. Tetrahedron 2005; 61: 321
- 1c Carson CA, Kerr MA. Chem. Soc. Rev. 2009; 38: 3051
- 1d Lebold TP, Kerr MA. Pure Appl. Chem. 2010; 82: 1797
- 1e Mel’nikov MY, Budynina EM, Ivanova OA, Trushkov IV. Mendeleev Commun. 2011; 21: 293
-
1f Schneider TF, Kaschel J, Werz DB. Angew. Chem. Int. Ed. 2014; 53: 5504
- 2a England DB, Kuss TD. O, Keddy RG, Kerr MA. J. Org. Chem. 2001; 66: 4704
- 2b Korotkov VS, Larionov OV, De Meijere A. Synthesis 2006; 3542
- 2c Fang J, Ren J, Wang ZW. Tetrahedron Lett. 2008; 49: 6659
- 2d Qu JP, Deng C, Zhou J, Sun XL, Tang Y. J. Org. Chem. 2009; 74: 7684
- 2e Chagarovskiy AO, Budynina EM, Ivanova OA, Grishin YK, Trushkov IV, Verteletskii PV. Tetrahedron 2009; 65: 5385
- 2f Novikov RA, Tomilov YV, Nefedov OM. Mendeleev Commun. 2012; 22: 181
- 2g Xiong H, Xu H, Liao S, Xie Z, Tang Y. J. Am. Chem. Soc. 2013; 135: 7851
- 2h Mackay WD, Fistikci M, Carris RM, Johnson JS. Org. Lett. 2014; 16: 1626
- 3a Carson CA, Kerr MA. J. Org. Chem. 2005; 70: 8242
- 3b Kang YB, Tang Y, Sun X.-L. Org. Biomol. Chem. 2006; 4: 299
-
3c Xing S, Pan W, Liu C, Ren J, Wang Z. Angew. Chem. Int. Ed. 2010; 49: 3215
- 4a Yu M, Pagenkopf BL. J. Am. Chem. Soc. 2003; 125: 8122
- 4b Yu M, Pagenkopf BL. Org. Lett. 2003; 5: 5099
- 4c Cui B, Ren J, Wang Z. J. Org. Chem. 2014; 79: 790
- 5a Christie SD. R, Davoile RJ, Elsegood MR. J, Fryatt R, Jones RC. F, Pritchard GJ. Chem. Commun. 2004; 2474
- 5b Pohlhaus PD, Johnson JS. J. Org. Chem. 2005; 70: 1057
- 5c Pohlhaus PD, Johnson JS. J. Am. Chem. Soc. 2005; 127: 16014
- 5d Gupta A, Yadav VK. Tetrahedron Lett. 2006; 47: 8043
- 5e Pohlhaus PD, Sanders SD, Parsons AT, Li W, Johnson JS. J. Am. Chem. Soc. 2008; 130: 8642
- 5f Parsons AT, Johnson JS. J. Am. Chem. Soc. 2009; 131: 3122
- 5g Christie SD. R, Cummins J, Elsegood MR. J, Dawson G. Synlett 2009; 257
- 6 Lebold TP, Leduc AB, Kerr MA. Org. Lett. 2009; 11: 3770
- 7 Young IS, Kerr MA. Angew. Chem. Int. Ed. 2003; 42: 3023
- 8a Ganton MD, Kerr MA. J. Org. Chem. 2004; 69: 8554
- 8b Sibi MP, Ma Z, Jasperse CP. J. Am. Chem. Soc. 2005; 127: 5764
- 8c Kang Y.-B, Sun X.-L, Tang Y. Angew. Chem. Int. Ed. 2007; 46: 3918
- 8d Perreault C, Goudreau SR, Zimmer LE, Charette AB. Org. Lett. 2008; 10: 689
-
8e Dias DA, Kerr MA. Org. Lett. 2009; 11: 3694
- 8f Sapeta K, Kerr MA. Org. Lett. 2009; 11: 2081
- 8g Ding Q, Wang Z, Wu J. Tetrahedron Lett. 2009; 50: 198
- 8h Wu L, Shi M. Chem. Eur. J. 2010; 16: 1149
- 8i Ivanova OA, Budynina EM, Chagarovskiy AO, Trushkov IV, Melnikov MY. J. Org. Chem. 2011; 76: 8852
- 8j Novikov RA, Korolev VA, Timofeev VP, Tomilov YV. Tetrahedron Lett. 2011; 52: 4996
- 8k Yang H.-B, Shi M. Org. Biomol. Chem. 2012; 10: 8236
- 8l Novikov RA, Tomilov YV. Helv. Chim. Acta 2013; 96: 2068
- 9 Gorbacheva EO, Tabolin AA, Novikov RA, Khomutova YA, Nelyubina YV, Tomilov YV, Ioffe SL. Org. Lett. 2013; 15: 350
- 10a Smirnov VO, Ioffe SL, Tishkov AA, Khomutova YA, Nesterov ID, Antipin MY, Smit WA, Tartakovsky VA. J. Org. Chem. 2004; 69: 8485
- 10b Khomutova YA, Smirnov VO, Mayr H, Ioffe SL. J. Org. Chem. 2007; 72: 9134
- 10c Smirnov VO, Sidorenkov AS, Khomutova YA, Ioffe SL, Tartakovsky VA. Eur. J. Org. Chem. 2009; 3066
- 10d Smirnov VO, Khomutova YA, Tartakovsky VA, Ioffe SL. Eur. J. Org. Chem. 2012; 3377
- 10e Mikhaylov AA, Dilman AD, Khomutova YA, Arkhipov DE, Korlyukov AA, Ioffe SL. Eur. J. Org. Chem. 2013; 5670
- 11 N-Silyloxy tetrahydro-1,2-oxazines with another range of substituents and other stereochemistry are available via silyl triflate promoted nucleophile addition of nucleophiles to six-membered cyclic nitronates, see ref. 10a,b.
- 12a Young IS, Williams JL, Kerr MA. Org. Lett. 2005; 7: 953
- 12b Sukhorukov AY, Ioffe SL. Chem. Rev. 2011; 111: 5004
- 13 For high invertion barrier in ONO systems, see: Rudchenko VF. Chem. Rev. 1993; 93: 725
- 14 See Supporting Information for details of X-ray crystal structure analysis. CCDC-995336 (for 3ca), 995333 (for 3ea), 995335 (for 3cb), 995334 (for 3cd), 995337 (for 5ea) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
- 15a Wanapun D, Van Gorp KA, Mosey NJ, Kerr MA, Woo TK. Can. J. Chem. 2005; 83: 1752
- 15b Sapeta K, Kerr MA. J. Org. Chem. 2007; 72: 8597
- 15c Karadeolian A, Kerr MA. J. Org. Chem. 2007; 72: 10251
- 16 Ioffe SL In Nitrile Oxides, Nitrones and Nitronates in Organic Synthesis . Feuer H. John Wiley and Sons; Chichester: 2008. 2nd ed. 509-513
- 17 Shitkin VM, Ioffe SL, Kashutina MV, Tartakovsky VA. Bull. Acad. Sci. USSR, Div. Chem. (Engl. Transl.) 1978; 2101 ; Izv. Akad. Nauk SSSR, Ser. Khim. 1977, 2266
-
18 Jackson SK, Karadeolian A, Driega AB, Kerr MA. J. Am. Chem. Soc. 2008; 130: 4196
- 19 The transformation 3 → 4 + 5 needs detailed investigation.
- 20a Reaction of nitroso benzene with diazoacetate under TfOH catalysis: Xu Z.-J, Zhu D, Zeng X, Wang F, Tan B, Hou Y, Lv Y, Zhong G. Chem. Commun. 2010; 46: 2504
- 20b Interaction of alkenylgold carbenoids with nitroso benzenes: Pagar VV, Jadhav AM, Liu R.-S. J. Am. Chem. Soc. 2011; 133: 20728
- 20c Nitroso + alkene/nitrone metathesis: Kang JY, Bugarin A, Connell BT. Chem. Commun. 2008; 44: 3522
For reviews, see:
Selected examples:
Selected examples:
Selected examples:
Selected examples:
For cyclodimerization of cyclopropanes, see:
In our opinion the closest literature data are: