Allylation Reactions of N,O-Heterocycles

Roderick W. Bates; Chi H. Tang; Yuting Tan; Siti Nurhayati binte Buang

doi:10.1055/s-0031-1290458

Synlett, Table of Contents

Synlett 2012; 23(15): 2266-2268
DOI: 10.1055/s-0031-1290458

letter

Allylation Reactions of N,O-Heterocycles

Authors

Roderick W. Bates*

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, 637371 Singapore, Singapore, Fax: +6567911961 Email: roderick@ntu.edu.sg
Chi H. Tang

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, 637371 Singapore, Singapore, Fax: +6567911961 Email: roderick@ntu.edu.sg
Yuting Tan

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, 637371 Singapore, Singapore, Fax: +6567911961 Email: roderick@ntu.edu.sg
Siti Nurhayati binte Buang

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, 637371 Singapore, Singapore, Fax: +6567911961 Email: roderick@ntu.edu.sg

Abstract

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Abstract

Iminium ions generated from isoxazolidines and tetrahydro-1,2-oxazines undergo allylation under Sakurai conditions. Allylated isoxazolidines are formed predominantly as the trans isomer, while oxazines are formed exclusively as the cis isomer.

Key words

heterocycles - allylation - stereoselectivity

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References

References and Notes
1 Bates RW, Boonsombat J, Lu Y, Nemeth JA, Sa-Ei K, Song P, Cai MP, Cranwell PB, Winbush SA. Pure Appl. Chem. 2008; 80: 681

For the use of isoxazolidines for β-amino acid synthesis, see:

2a Fuller AA, Chen B, Minter AR, Mapp AK. Synlett 2004; 1409
2b Examples in sedum alkaloid synthesis may be found in: Bates RW, Sa-Ei K. Tetrahedron 2002; 58: 5957

3 Bates RW, Sa-Ei K. Org. Lett. 2002; 4: 4225

4a Bates RW, Nemeth J, Snell R. Synthesis 2008; 1033
4b Bates RW, Lu Y. J. Org. Chem. 2009; 74: 9460
4c Bates RW, Lu Y. Org. Lett. 2010; 12: 3938

5 For another noncycloaddition route to isoxazolidines, see: Lemen GS, Giampietro NC, Hay MB, Wolfe JP. J. Org. Chem. 2009; 74: 2533
6 Also, 3,4-trans is favoured: Bates RW, Lim CJ. Synlett 2010; 866
7 Bates RW, Snell RH, Winbush SA. Synlett 2008; 1042

For recent reviews of N-acyliminium ion chemistry, see:

8a Speckamp N, Moolenaar MJ. Tetrahedron 2000; 56: 3817
8b Yazici A, Pyne SG. Synthesis 2009; 339
8c Yazici A, Pyne SG. Synthesis 2009; 513

9 Niu D, Zhao H, Doshi A, Zhao K. Synlett 1998; 979
10 Freire Castro FJ, Vila MM, Jenkins PR, Sharma ML, Tustin G, Fawcett J, Russell DR. Synlett 1999; 798

Certain 3-methoxyisoxazolidines and derivatives, prepared by 1,3-dipolar cycloaddition, have been claimed as anti-acne agents:

11a Castelhano AL, DeYoung LM, Krantz A, Pliura DH, Venuti MC. US 4912120 A1, 1990
11b Castelhano AL, Krantz A, Pliura DH, Venuti MC, DeYoung LM. EP 237082 B1, 1991

12 Grochowski E, Jurczak J. Synthesis 1976; 682
13 5-Hydroxyisoxazolidines have also been prepared by the reaction between hydroxylamines and α,β-unsaturated aldehydes: Zelenin KN, Motorina IA, Sviridova LA, Bezhan IP, Ershov AY, Golubeva GA, Bundel YG. Chem. Heterocycl. Compd. 1988; 23: 1018
14 Acid-catalysed exchange in 3-hydroxyisoxazolidines has been reported: Motorina IA, Sviridova LA, Golubeva GA, Zelenin KN, Bezhan IP, Ershov AY, Bundel YG. Chem. Heterocycl. Compd. 1989; 24: 1373
15 Details have been deposited with the Cambridge Crystallographic Data Centre and may be obtained at http://www.ccdc.cam.ac.uk. CCDC deposition numbers: 7b: 878055 and 9: 877996
16 Characterisation Data for Compound 7b Mp 69–71 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.25–7.50 (10 H, m), 5.35 (1 H, br), 5.33 (br d J = 12.0 Hz), 5.19 (d, J = 12.0 Hz), 4.72 (br s, 1 H), 3.35 (3 H, br s), 2.35 (1 H, app dq, J = 5.0, 12.0 Hz), 2.05–2.10 (1 H, m), 1.88–2.00 (1 H, m), 1.79–1.84 (1 H, m), 1.80–2.40 (4 H, m)
17 Spectroscopic Data for Compound trans-8a ¹H NMR (400 MHz, CDCl₃): δ = 7.37–7.28 (5 H, m), 5.85 (1 H, ddt, J = 17.3, 10.2, 7.1 Hz), 5.27 (1 H, t, J = 6.6 Hz), 5.21–5.14 (2 H, m), 4.39 (1 H, tt, J = 8.0, 5.0 Hz); 3.68 (3 H, s), 2.65–2.38 (4 H, m). ¹³C NMR (100 MHz, CDCl₃): δ = 157.5, 138.5, 134.0, 128.8, 118.4, 81.7, 59.0, 53.2, 40.0, 39.1

18a Cicchi S, Goti A, Brandi A, Guarna A, Sarlos FD. Tetrahedron Lett. 1990; 31: 3351
18b Mulvihill MJ, Gage JL, Miller MJ. J. Org. Chem. 1998; 63: 3357

19 Spectroscopic Data for Compound 10c ¹H NMR (400 MHz, CDCl₃): δ = 5.67–5.78 (m, 1 H), 5.15 (1 H, ddd, J = 17.0, 3.0, 1.5 Hz), 5.08 (1 H, dt, J = 10.0, 1.0 Hz), 4.73 (1 H, br d), 4.35 (1 H, br), 3.78 (3 H, s), 2.70 (1 H, app quin, J = 7.0 Hz), 2.44 (1 H, app quin, J = 7.0 Hz), 2.10–2.20 (1 H, m), 1.9.0–2.05 (1 H, m), 1.8.0–1.90 (2 H, m). ¹³C NMR (400 MHz, CDCl₃): δ = 25.6, 26.6, 34.3, 53.2, 83.3 (br), 117.6, 126.6, 128.5, 128.6, 134.8, 139.4, 156.1
20 Stereoelectronic Effects in Organic Chemistry . Deslongchamps P. Pergamon Press; Oxford: 1983: 211-221
21 All compounds used in this study were racemic