Ring-Rearrangement Metathesis of Substituted 2-Aminonorbornenes

Adam E. Nadany; John E. Mckendrick

doi:10.1055/s-2007-982573

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 2007(11): 1663-1666
DOI: 10.1055/s-2007-982573

LETTER

Ring-Rearrangement Metathesis of Substituted 2-Aminonorbornenes

Adam E. Nadany, John E. Mckendrick*
Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK
Fax: +44(118)3786331; e-Mail: j.e.mckendrick@reading.ac.uk;

Further Information

Publication History

Received 3 April 2007
Publication Date:
25 June 2007 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

In this report we describe the ring-rearrangement metathesis of 2-aminonorbornene derivatives. An efficient ruthenium-catalysed metathesis reaction occurs with a wide range of pendent alkenes and alkynes to generate bicyclic amines and amides.

Key words

metathesis - Diels-Alder reaction - piperidine alkaloids

References and Notes

1a Bazan GC. Oskam JH. Cho HN. Park LY. Schrock RR. J. Am. Chem. Soc. 1991, 113: 6889

Google Scholar
1b Bazan GC. Khosravi E. Schrock RR. Feast WJ. Gibson VC. O’Regan MB. Thomas JK. Davis WM. J. Am. Chem. Soc. 1990, 112: 8378

Google Scholar
1c Schrock RR. Tetrahedron 1999, 55: 8141

Google Scholar
1d Schrock RR. Acc. Chem. Res. 1990, 23: 158

Google Scholar
2a Nguyen ST. Grubbs RH. Ziller JW. J. Am. Chem. Soc. 1993, 115: 9858

Google Scholar
2b Scwabb P. Grubbs RH. Ziller JW. J. Am. Chem. Soc. 1996, 118: 100

Google Scholar
3a Garber SB. Kingsbury JS. Gray BL. Hoveyda AH. J. Am. Chem. Soc. 2000, 122: 8168

Google Scholar
3b Dunne AM. Mix S. Blechert S. Tetrahedron 2003, 59: 2733

Google Scholar
For reviews on the history, synthesis, and activity of the molybdenum-based metathesis catalysts, see:
4a Schrock RR. Hoveyda AH. Angew. Chem. Int. Ed. 2003, 42: 4592

Crossref PubMed Google Scholar
For recent reviews on ruthenium-based RCM, see:
4b Fürstner A. Angew. Chem. Int. Ed. 2000, 39: 3012

Crossref PubMed Google Scholar
4c Trnka TM. Grubbs RH. Acc. Chem. Res. 2001, 34: 18

Crossref PubMed Google Scholar
5 Blechert S. Connon SJ. Angew. Chem. Int. Ed. 2003, 42: 1900

Google Scholar
6a Stragies R. Blechert S. Tetrahedron 1999, 8179

Crossref Google Scholar
6b Pfeiffer MWB. Phillips AJ. J. Am. Chem. Soc. 2005, 127: 5334

Crossref Google Scholar
6c Winkler JD. Asselin SM. Shepard S. Yuan J. Org. Lett. 2004, 6: 3821

Crossref Google Scholar
6d Wrobleski A. Sahasrabudhe K. Aube J. J. Am. Chem. Soc. 2004, 126: 5475

Crossref Google Scholar
6e Chandler CL. Phillips AJ. Org. Lett. 2005, 7: 3493

Crossref Google Scholar
6f Yasui H. Yamamoto S. Saaki D. Kawasaki S. Watanabe G. Tadano K.-I. J. Org. Chem. 2004, 69: 8789

Crossref Google Scholar
6g Boyer F.-D. Hanna I. Ricard L. Org. Lett. 2004, 6: 1817

Crossref Google Scholar
6h Quinn KJ. Isaacs AK. Arvary RA. Org. Lett. 2004, 6: 4143

Crossref Google Scholar
6i Lesma G. Crippa S. Danieli B. Passarella D. Sacchetti A. Silvani A. Virdis A. Tetrahedron 2004, 60: 6437

Crossref Google Scholar
6j Csaky AG. Medel R. Murcia MC. Plumet J. Helv. Chim. Acta 2005, 88: 1387

Crossref Google Scholar
7 Handbook of Metathesis Vol. 2: Grubbs RH. Wiley-VCH; Weinheim: 2003. Chap. 2-4. p.151-175

Google Scholar
8 Arjona O. Csaky AG. Murica MC. Plumet J. Tetrahedron Lett. 2000, 41: 9777

Crossref Google Scholar
9 Ruckert A. Reisele D. Blechert S. Tetrahedron Lett. 2001, 42: 5245

Google Scholar
10 Hagiwara H. Katsumi T. Endou S. Hoshi T. Suzuki T. Tetrahedron 2002, 58: 6651

Crossref Google Scholar
11a Voightmann U. Blechert S. Synthesis 2000, 893

Google Scholar
11b Kitamura T. Mori M. Org. Lett. 2001, 3: 1161

Google Scholar
11c Ovaa H. Stapper C. van der Marel GA. Overkleeft HS. van Boom JH. Blechert S. Tetrahedron 2002, 58: 7503

Google Scholar
11d Arjona O. Csaky AG. Medel R. Plumet J. J. Org. Chem. 2002, 67: 1380

Google Scholar
11e Arjona O. Csaky AG. Murcia C. Plumet J. ARKIVOC 2002, (v): 171

Google Scholar
11f Arjona O. Csaky AG. Leon V. Medel R. Plumet J. Tetrahedron Lett. 2004, 45: 565

Google Scholar
11g Holub N. Neidhofer J. Blechert S. Org. Lett. 2005, 7: 1227

Google Scholar
11h Groaz E. Banti D. North M. Tetrahedron Lett. 2007, 48: 1927

Google Scholar
12a Maechling S. Norman SE. Mckendrick JE. Basra S. Knoppner K. Blechert S. Tetrahedron Lett. 2006, 47: 189

Crossref Google Scholar
12b Nadany AE. Mckendrick JE. Synlett 2006, 2139

Crossref Google Scholar
12c Nadany AE. Mckendrick JE. Tetrahedron Lett. 2007, 48: 4071

Crossref Google Scholar
13a Krieger H. Suom. Kemistil., B 1963, 36: 68

Crossref Google Scholar
13b Freeman PK. Balls DM. Brown DJ. J. Org. Chem. 1968, 33: 2211

Crossref Google Scholar
14a Longobardi M. Schenone P. Bargagna A. Berrino L. Matera C. Marmo E. Farmco Ed. Sci. 1985, 40: 152

Crossref Google Scholar
14b Abdel-Magid AF. Carson KG. Harris BD. Maryanoff CA. Shah RD. J. Org. Chem. 1996, 61: 3849

Crossref Google Scholar
Analogous reduction of norborn-5-en-2-one:
14c Mayo P. Orlova G. Goddard JD. Tam W. J. Org. Chem. 2001, 66: 5182

Crossref Google Scholar
14d Oppolzer W. Chapuis C. Dupuis D. Guo M. Helv. Chim. Acta 1985, 68: 2100

Crossref Google Scholar
16 Fürstner A. Langemann K. J. Am. Chem. Soc. 1997, 119: 9130

Crossref Google Scholar
17 Kinoshita A. Sakakibara N. Mori M. J. Am. Chem. Soc. 1997, 119: 12388

Crossref Google Scholar
19 Parham WE. Hunter WT. Hanson R. J. Am. Chem. Soc. 1951, 73: 5068

Crossref Google Scholar
20a Fangzheng L. Warshakoon NC. Miller MJ. J. Org. Chem. 2004, 69: 8836

Crossref Google Scholar
20b Kozikowski AP. Park P. J. Am. Chem. Soc. 1985, 107: 1736

Crossref Google Scholar
20c Kozikowski AP. Park P. J. Org. Chem. 1990, 55: 4668

Crossref Google Scholar
20d Flann CJ. Overman LE. J. Am. Chem. Soc. 1987, 109: 6115

Crossref Google Scholar
20e Yamada H. Aoyagi S. Kibayashi C. J. Am. Chem. Soc. 1996, 118: 1054

Crossref Google Scholar
20f Huang S. Comins DL. Chem. Commun. 2000, 569

Crossref Google Scholar

15

Spectroscopic Data for 5a
¹H NMR (400 MHz, CDCl₃, 70 °C): δ = 1.35-1.38 (m, 1 H, CH₂CHN), 1.35-1.38 (m, 1 H, CH₂CHCHN), 2.12-2.33 (m, 1 H, CH₂CHN), 2.12-2.33 (m, 1 H, CH₂CHCHN), 2.12-2.33 (m, 1 H, CHCH₂CHN), 2.90-2.94 (m, 1 H, CHCHN), 3.69 (dt, 1 H, CHN, J = 10.5, 6.5 Hz), 4.06 (d, 1 H, CH₂Ph, J = 15.0 Hz), 4.90-5.03 (m, 2 H, CH=CH₂), 5.29 (d, 1 H, CH₂Ph, J = 15.0 Hz), 5.71 (ddd, 1 H, CH=CH₂, J = 17.0, 13.0, 7.0 Hz), 5.87 (dd, 1 H, HC=CH, J = 10.0, 2.5 Hz), 6.24 (dd, 1 H, HC=CH, J = 10.0, 3.0 Hz), 7.25-7.33 (m, 5 H, 5 × ArH). ¹³C NMR (100 MHz, CDCl₃, 70 °C): δ = 36.6 (CHCHN), 38.6 (CH₂CHCHN), 39.0 (CH₂CHN), 40.1 (CHCH₂CHN), 48.5 (CH₂Ph), 58.7 (CHN), 114.5 (CH=CH₂), 122.0 (HC=CH), 127.8 (1 × ArH), 128.4 (2 × ArH), 129.0 (2 × ArH), 138.0 (1 × Ar), 141.2 (CH=CH₂), 143.4 (HC=CH), 162.7 (C=O). IR (thin film): 1610 (C=C), 1667 (C=O), 2955 (sat. C-H) cm^-1. MS: m/z calcd: 254.1546 [MH⁺]; found: 254.1546.

18

General Procedure for Olefin Metathesis, Synthesis of 8c
A flask was charged with toluenesulfonyl amine 7c (91 mg, 0.3 mmol) and CH₂Cl₂ (90 mL). Ethene gas was bubbled through the solution for 20 s. Then, Grubbs I catalyst (25 mg, 0.03 mmol) was added to the reaction. A balloon filled with ethene gas was placed over the flask and the reaction was allowed to stir at r.t. overnight. The reaction mixture was then concentrated and subjected to column chromatography eluting PE-Et₂O (19:1 to 4:1) to furnish 8c as a colourless oil (89 mg), 99% yield. ¹H NMR (400 MHz, CDCl₃): δ = 1.11 (ddd, 1 H, CH₂CHN, J = 13.5, 8.0, 4.0 Hz), 1.33 (dd, 1 H, H₂CHCHC=CH, J = 14.5, 7.5 Hz), 1.66 (dt, 1 H, H₂CHCHC=CH, J = 12.0, 6.5 Hz), 2.13 (td, 1 H, CH₂CHN, J = 16.0, 13.5 Hz), 2.41 (s, 3 H, CH₃), 2.41-2.43 (m, 1 H, HCHC=CH), 2.60-2.65 (br m, 1 H, HCHC=CH₂), 3.45-3.50 (m, 1 H, CH₂N), 4.06-4.10 (m, 1 H, CH₂N), 4.37 (dt, CHN, 1 H, J = 12.0, 7.0 Hz), 4.83-4.94 (m, 2 H, HC=CH₂), 5.51-5.61 (m, 2 H, HC=CH), 5.64 (ddd, 1 H, HC=CH₂, J = 17.5, 10.0, 7.5 Hz), 7.30 (app. d, 2 H, ArH, J = 8.5 Hz), 7.70 (app. d, 2 H, ArH, J = 7.5 Hz). ¹³C NMR (100 MHz, CDCl₃): δ = 21.5 (CH₃), 32.0 (H₂CHCHC=CH), 35.4 (HCHC=CH₂), 35.8 (CH₂CHN), 39.4 (CH₂N), 39.7 (HCHC=CH), 55.6 (CHN), 113.1 (HC=CH₂), 120.0 (HC=CH), 127.2 (2 × ArCH), 129.6 (2 × ArCH), 130.8 (HC=CH), 136.8 (1 × ArC), 142.4 (HC=CH₂), 143.2 (1 × Ar). IR (thin film): 1162, 1384 (SO₂), 2975 (sat. C-H) cm^-1. MS: m/z calcd for 303.1290 [M⁺]; found: 303.1293.