Intramolecular Oxidative Pd(II)-Catalyzed
Alkoxylation of 3-Aza-5-alkenols with O2 as Sole Oxidant:
Mild Conditions for the Synthesis of 1,4-Oxazine Derivatives

Gianluigi Broggini; Egle M. Beccalli; Elena Borsini; Andrea Fasana; Gaetano Zecchi

doi:10.1055/s-0030-1259295

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

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2011(2): 227-230
DOI: 10.1055/s-0030-1259295

LETTER

Intramolecular Oxidative Pd(II)-Catalyzed Alkoxylation of 3-Aza-5-alkenols with O₂ as Sole Oxidant: Mild Conditions for the Synthesis of 1,4-Oxazine Derivatives

Gianluigi Broggini*^a, Egle M. Beccalli^b, Elena Borsini^b, Andrea Fasana^a, Gaetano Zecchi^a
^a Dipartimento di Scienze Chimiche e Ambientali, Università degli Studi dell’Insubria, Via Valleggio 11, 22100 Como, Italy
Fax: +39(031)2386449; e-Mail: gianluigi.broggini@uninsubria.it;
^b DISMAB, Sezione di Chimica Organica ‘A. Marchesini’, Università di Milano, Via Venezian 21, 20133 Milano, Italy

Further Information

Publication History

Received 17 October 2010
Publication Date:
04 January 2011 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Synthesis of 1,4-2H-oxazine derivatives was performed by Pd(II)-catalyzed aerobic oxidative cyclization of 3-aza-5-alkenols, prepared from easily available 1,2-amino alcohols. The reaction proceeds in very mild conditions with a simple catalytic system consisting of PdCl₂(MeCN)₂ in THF at room temperature with molecular oxygen as the sole stoichiometric oxidant.

Key words

palladium - heterocycles - alkenols - alkoxylation - molecular oxygen

References and Notes

1a Beccalli EM. Broggini G. Martinelli M. Sottocornola S. Chem. Rev. 2007, 107: 5318

Google Scholar
1b Kotov V. Scarborough CC. Stahl SS. Inorg. Chem. 2007, 46: 1910

Google Scholar
For some recent examples, see:
2a Jiang H. Feng Z. Wang A. Liu X. Chen Z. Eur. J. Org. Chem. 2010, 1227

Google Scholar
2b Xu Y.-H. Wang W.-J. Wen Z.-K. Hartley JJ. Loh T.-P. Tetrahedron Lett. 2010, 51: 3504

Google Scholar
2c Yang Y. Cheng K. Zhang Y. Org. Lett. 2009, 11: 5606

Google Scholar
2d Aouf C. Thiery E. Le Bras J. Muzart J. Org. Lett. 2009, 11: 4096

Google Scholar
2e Maehara A. Satoh T. Miura M. Tetrahedron 2008, 64: 5982

Google Scholar
2f Thiery E. Harakat D. Le Bras J. Muzart J. Organometallics 2008, 27: 3996

Google Scholar
For some recent examples, see:
3a Jiang F. Wu Z. Zhang W. Tetrahedron Lett. 2010, 51: 5124

Google Scholar
3b Liu X. Hii KK. Eur J. Org. Chem. 2010, 5181

Google Scholar
3c Yin G. Wu Y. Liu G. J. Am. Chem. Soc. 2010, 132: 11978

Google Scholar
3d Reed SA. Mazzotti AR. White MC. J. Am. Chem. Soc. 2009, 131: 11701

Google Scholar
3e Tsujihara T. Shinohara T. Takenaka K. Takizawa S. Onitsuka K. Hatanaka M. Sasai H. J. Org. Chem. 2009, 74: 9274

Google Scholar
3f Jensen KH. Pathak TP. Zhang Y. Sigman MS. J. Am. Chem. Soc. 2009, 131: 17074

Google Scholar
For some examples by using Cu(OAc)₂ as oxidant:
4a Koubachi J. Berteina-Raboin S. Mouaddib A. Guillaumet G. Synthesis 2009, 271

Google Scholar
4b García-Rubia A. Gómez Arrayás R. Carretero JC. Angew. Chem. Int. Ed. 2009, 48: 6511

Google Scholar
For some examples by using Ag(I) as oxidant:
4c Miyasaka M. Hirano K. Satoh T. Miura M. J. Org. Chem. 2010, 75: 5421

Google Scholar
4d Wu T. Yin G. Liu G. J. Am. Chem. Soc. 2009, 131: 16354

Google Scholar
For some examples by using H₂O₂ as oxidant:
4e Yin G., Liu G.; Angew. Chem. Int. Ed.; 2008, 47: 5442

Google Scholar
For some examples by using BQ as oxidant:
4f Han X. Lu X. Org. Lett. 2009, 11: 2381

Google Scholar
4g Takenaka K. Mohanta SC. Patil ML. Rao CVL. Takizawa S. Suzuki T. Sasai H. Org. Lett. 2010, 12: 3480

Google Scholar
For some examples by using hypervalent iodine as oxidant:
4h Desai LV. Stowers KJ. Sanford MS.
J. Am. Chem. Soc. 2008, 130: 13285

Google Scholar
4i Rodriguez A. Moran WJ. Eur J. Org. Chem. 2009, 1313

Google Scholar
For some examples by using CuCl₂ as oxidant:
4j Christie SDR. Warrington AD. Lunniss CJ. Synthesis 2009, 148

Google Scholar
4k Liu C. Widenhoefer RA. Chem. Eur. J. 2006, 12: 2371

Google Scholar
4l Szolcsányi P. Gracza T. Chem. Commun. 2005, 3948

Google Scholar
For some reviews, see:
5a Stahl SS. Angew. Chem. Int. Ed. 2004, 43: 3400

Google Scholar
5b Gligorich KM. Sigman MS. Angew. Chem. Int. Ed. 2006, 45: 6612

Google Scholar
5c Piera J. Bäckvall J.-E. Angew. Chem. Int. Ed. 2008, 47: 3506

Google Scholar
5d Gligorich KM. Sigman MS. Chem. Commun. 2009, 3854

Google Scholar
For some papers, see:
6a Liégault B. Fagnou K. Organometallics 2008, 27: 4841

Google Scholar
6b Yin G. Liu G. Wu L. Angew. Chem. Int. Ed. 2008, 47: 4733

Google Scholar
6c Zhang Z. Tan J. Wang Z. Org. Lett. 2008, 10: 173

Google Scholar
6d Wang A. Jiang H. Chen H. J. Am. Chem. Soc. 2009, 131: 3846

Google Scholar
6e Yip K.-T. Zhu N.-Y. Yang D. Org. Lett. 2009, 11: 1911

Google Scholar
6f He W. Yip K.-T. Zhu N.-Y. Yang D. Org. Lett. 2009, 11: 5626

Google Scholar
6g Wu L. Qiu S. Liu G. Org. Lett. 2009, 11: 2707

Google Scholar
6h Jia X. Zhang S. Wang W. Luo F. Cheng J. Org. Lett. 2009, 11: 3120

Google Scholar
6i Watanabe T. Oishi S. Fujii N. Ohno H. J. Org. Chem. 2009, 74: 4720

Google Scholar
6j Blangetti M. Deagostino A. Prandi C. Tabasso S. Venturello P. Org. Lett. 2009, 11: 3914

Google Scholar
6k Wang A. Jiang H. J. Org. Chem. 2010, 75: 2321

Google Scholar
6l McDonald RI. Stahl SS. Angew. Chem. Int. Ed. 2010, 49: 5529

Google Scholar
6m Zhu M.-K. Zhao J.-F. Loh T.-P. J. Am. Chem. Soc. 2010, 132: 6284

Google Scholar
7a Gabriele B. Salerno G. Costa M. Synlett 2004, 2468

Google Scholar
7b Hövelmann CH. Streuff J. Brelot L. Muñiz K. Chem. Commun. 2008, 2334

Google Scholar
7c Zhang Z. Zhang J. Tan J. Wang Z. J. Org. Chem. 2008, 73: 5180

Google Scholar
7d Muñiz K. Hövelmann CH. Campos-Gómez E. Barluenga J. González JM. Streuff J. Nieger M. Chem. Asian J. 2008, 3: 776

Google Scholar
7e Houlden CE. Bailey CD. Ford JG. Gagné MR. Lloyd-Jones GC. Booker-Milburn KI. J. Am. Chem. Soc. 2008, 130: 10066

Google Scholar
7f Muñiz K. Streuff J. Chávez P. Hövelmann CH. Chem. Asian J. 2008, 3: 1248

Google Scholar
7g Della Ca’N. Campanini F. Gabriele B. Salerno G. Massera C. Costa M. Adv. Synth. Catal. 2009, 2423

Google Scholar
7h Alladoum J. Vrancken E. Mangeney P. Roland S. Kadouri-Puchot C. Org. Lett. 2009, 11: 3746

Google Scholar
7i Kawamura Y. Kawano Y. Matsuda T. Ishitobi Y. Hosokawa T. J. Org. Chem. 2009, 74: 3048

Google Scholar
7j Xiao Q. Wang W.-H. Liu G. Meng F.-K. Chen J.-H. Yang Z. Shi Z.-J. Chem. Eur. J. 2009, 15: 7292

Google Scholar
7k Rice GT. White MC. J. Am. Chem. Soc. 2009, 131: 11707

Google Scholar
7l Sibbald PA. Michael FE. Org. Lett. 2009, 11: 1147

Google Scholar
7m Lu Y. Wang D.-H. Engle KM. Yu J.-Q. J. Am. Chem. Soc. 2010, 132: 5916

Google Scholar
8a Beccalli EM. Broggini G. Tetrahedron Lett. 2003, 44: 1919

Google Scholar
8b Abbiati G. Beccalli EM. Broggini G. Zoni C. J. Org. Chem. 2003, 68: 7625

Google Scholar
8c Beccalli EM. Broggini G. Paladino G. Penoni A. Zoni C. J. Org. Chem. 2004, 69: 5627

Google Scholar
8d Beccalli EM. Broggini G. Martinelli M. Paladino G. Tetrahedron 2005, 61: 1077

Google Scholar
8e Abbiati G. Beccalli EM. Broggini G. Martinelli M. Paladino G. Synlett 2006, 73

Google Scholar
8f Beccalli EM. Borsini E. Broggini G. Rigamonti M. Sottocornola S. Synlett 2008, 1053

Google Scholar
8g Beccalli EM. Borsini E. Broggini G. Palmisano G. Sottocornola S. J. Org. Chem. 2008, 73: 4746

Google Scholar
9 Achari B. Mandal SB. Dutta PK. Chowdhury C. Synlett 2004, 2449

Article in Thieme Connect Google Scholar
10 Chen C.-T. Kuo J.-H. Pawar VD. Munot YS. Weng S.-S. Ku C.-H. Liu C.-Y. J. Org. Chem. 2005, 70: 1188

Crossref Google Scholar
12 Maki Y. Shimada K. Sako M. Kitade Y. Hirota K. Chem. Pharm. Bull. 1988, 36: 1714

Crossref Google Scholar
13a Gross JL. Tetrahedon Lett. 2003, 44: 8563

Google Scholar
13b Thiery E. Chevrin C. Le Bras J. Hakarat D. Muzart J. J. Org. Chem. 2007, 72: 1859

Google Scholar
13c Fan J. Wan C. Wang Q. Gao L. Zheng X. Wang Z. Org. Biomol. Chem. 2009, 7: 3168

Google Scholar
13d Nishiwaki N. Kamimura R. Shono K. Kawakami T. Nakayama K. Nishino K. Nakayama T. Takahashi K. Nakamura A. Hosokawa T. Tetrahedon Lett. 2010, 51: 3590

Google Scholar

11

Experimental Procedure
A solution of 4 (1.0 mmol), PdCl₂(MeCN)₂ (0.05 mmol, 13 mg), in THF (5 mL) was stirred under oxygen atmosphere for 5 h at r.t.. The solvent was evaporated under reduced pressure. The crude mixture was diluted with brine (10 mL) and extracted with CH₂Cl₂ (2 × 25 mL). The organic layer was dried over Na₂SO₄ and the solvent removed under reduced pressure. The residue was chromatographed on a silica gel column with light PE-EtOAc (5:1) as eluent to give 5 (75%).
Data for 4-Acetyl-6-methyl-3,4-dihydro-2 H -1,4-oxazine (5) Colourless oil. IR (nujol): 1676 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 1.75 (3 H, s), 2.12 (3 H, s), 3.48 (2 H, t, J = 4.7 Hz), 3.55 (2 H, t, J = 4.7 Hz), 5.89 (1 H, s). ^¹³C NMR (100 MHz, CDCl₃): δ = 17.9 (q), 22.0 (q), 43.1 (t), 64.1 (t), 98.9 (d), 137.9 (s), 163.7 (s). MS: m/z = 141 [M⁺]. Anal. Calcd for C₇H₁₁NO₂: C, 59.56; H, 7.85; N, 9.92. Found C, 59.33; H, 7.96; N, 9.88.

14

Reaction conditions used to attempt the isomerization process: (i) PdCl₂ (10 mol%) in H₂O-MeOH (1:1) at 80 ˚C for 24 h; (ii) PdCl₂(TMEDA) (10 mol%) in H₂O-MeOH (1:1) at 80 ˚C for 24 h; (iii) PdCl₂(MeCN)₂ (10 mol%) in CH₂Cl₂ at r.t. for 24 h.