1,2-Aminothioethers Derived from Ephedrine and Pseudoephedrine: Heterobidentate Ligands for the Palladium-Catalysed Asymmetric Allylic Substitution Reaction

Philip C. Bulman Page; Harry Heaney; Serge Reignier; Gerasimos A. Rassias

doi:10.1055/s-2003-36221

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 2003(1): 0022-0028
DOI: 10.1055/s-2003-36221

LETTER

1,2-Aminothioethers Derived from Ephedrine and Pseudoephedrine: Heterobidentate Ligands for the Palladium-Catalysed Asymmetric Allylic Substitution Reaction

Philip C. Bulman Page*, Harry Heaney, Serge Reignier, Gerasimos A. Rassias
Department of Chemistry, Loughborough University, Loughborough, Leicestershire LE11 3TU, England
Fax: +44(1509)223926; e-Mail: p.c.b.page@lboro.ac.uk;

Further Information

Publication History

Received 25 October 2002
Publication Date:
18 December 2002 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Heterobidentate sulfide-tertiary amine ligands incorporating 1,2-aminothioethers derived from ephedrine and pseudoephedrine have been prepared and used successfully in the palladium-catalysed asymmetric allylic substitution reaction, giving ees of up to 89%. The stereoelectronic effects operating in the reactions are discussed.

Key words

ephedrine - heterobidentate ligands - allylic substitution

References

1a Trost BM. Strege PE. J. Am. Chem. Soc. 1977, 99: 1649

Crossref Google Scholar
1b Trost BM. van Vranken DL. Bingel CJ. J. Am. Chem. Soc. 1992, 114: 9327

Crossref Google Scholar
1c Trost BM. Bunt RC. J. Am. Chem. Soc. 1994, 116: 4089

Crossref Google Scholar
1d Trost BM. van Vranken DL. Chem. Rev. 1996, 96: 395

Crossref Google Scholar
1e Trost BM. Toste FD. J. Am. Chem. Soc. 1998, 120: 9074

Crossref Google Scholar
See, for example:
2a Hayashi T. Pure Appl. Chem. 1988, 60: 7

Crossref Google Scholar
2b Hayashi T. Yamamoto A. Ito Y. Nishioka E. Miura H. Yanagi K. J. Am. Chem. Soc. 1989, 111: 6301

Crossref Google Scholar
2c Hayashi T. Kishi K. Yamamoto A. Ito Y. Tetrahedron Lett. 1990, 31: 1743

Crossref Google Scholar
2d Yamaguchi M. Shima T. Yamagishi T. Hida M. Tetrahedron: Asymmetry 1991, 2: 663

Crossref Google Scholar
2e Pfaltz A. Acc. Chem. Res. 1993, 26: 339

Crossref Google Scholar
2f Imai Y. Zhang W. Kida T. Nakatsuji Y. Ikeda I. Tetrahedron Lett. 1998, 39: 4343

Crossref Google Scholar
2g Wiese B. Helmchen G. Tetrahedron Lett. 1998, 39: 5727

Crossref Google Scholar
2h Vyskocil S. Smrcina M. Hanus V. Polásek M. Kocovsky P. J. Org. Chem. 1998, 63: 7738

Crossref Google Scholar
2i Suzuki Y. Ogata Y. Hiroi K. Tetrahedron: Asymmetry 1999, 10: 1219

Crossref Google Scholar
2j Chelucci G. Gladiali S. Saba A. Tetrahedron: Asymmetry 1999, 10: 1393

Crossref Google Scholar
2k Anderson JC. Cubbon RJ. Harling JD. Tetrahedron: Asymmetry 1999, 10: 2829

Crossref Google Scholar
3a Dierkes P. Ramdeehul S. Barloy L. De Cian A. Fischer J. Kamer PCJ. van Leeuwen PWNM. Osborn JA. Angew. Chem. Int. Ed. 1998, 37: 3116

Crossref Google Scholar
3b Ramdeehul S. Dierkes P. Aguado R. Kamer PCJ. van Leeuwen PWNM. Osborn JA. Angew. Chem. Int. Ed. 1998, 37: 3118

Crossref Google Scholar
4 Trost BM. Hachiya I. J. Am. Chem. Soc. 1998, 120: 1104

Crossref Google Scholar
5 Evans DA. Woerpel KA. Hinman MM. Faul MM. J. Am. Chem. Soc. 1991, 113: 726

Google Scholar
6 von Matt P. Pfaltz A. Angew. Chem., Int. Ed. Engl. 1993, 32: 566

Google Scholar
7 Sprinz J. Helmchen G. Tetrahedron Lett. 1993, 34: 1769

Crossref Google Scholar
8 Dawson GJ. Frost CG. Williams JMJ. Coote SJ. Tetrahedron Lett. 1993, 34: 3149

Crossref Google Scholar
9 Zhang W. Hirao T. Ikeda I. Tetrahedron Lett. 1996, 37: 4545

Google Scholar
10 Lee S.-G. Lim CW. Song CE. Kim KM. Jun CH. J. Org. Chem. 1999, 64: 4445

Crossref Google Scholar
11a Yang H. Khan MA. Nicholas KM. Organometallics 1993, 12: 3485

Article in Thieme Connect Google Scholar
11b von Matt P. Loiseleur O. Koch G. Pfaltz A. Lefeber C. Feucht T. Helmchen G. Tetrahedron: Asymmetry 1994, 5: 573

Article in Thieme Connect Google Scholar
11c Burckhardt U. Hintermann L. Schnyder A. Togni A. Organometallics 1995, 14: 5415

Article in Thieme Connect Google Scholar
11d Saitoh A. Misawa M. Morimoto T. Synlett 1999, 483

Article in Thieme Connect Google Scholar
12 Brown JM. Hulmes DI. Guiry PJ. Tetrahedron 1994, 50: 4493

Google Scholar
13a Åkermark B. Hansson S. Krakenberger B. Vitagliano A. Zetterberg K. Organometallics 1984, 3: 679

Crossref Google Scholar
13b Åkermark B. Krakenberger B. Hansson S. Vitagliano A. Organometallics 1987, 6: 620

Crossref Google Scholar
13c Åkermark B. Hansson S. Vitagliano A. J. Am. Chem. Soc. 1990, 112: 4587

Crossref Google Scholar
14a Evans DA. Campos KR. Tedrow JS. Michael FE. Gagné MR. J. Org. Chem. 1999, 64: 2994

Crossref Google Scholar
14b Hiroi K. Suzuki Y. Kawagishi R. Tetrahedron Lett. 1999, 40: 715

Crossref Google Scholar
14c Hiroi K. Suzuki Y. Abe I. Tetrahedron: Asymmetry 1999, 10: 1173

Crossref Google Scholar
14d Koning B. Meetsma A. Kellogg RM. J. Org. Chem. 1998, 63: 5533

Crossref Google Scholar
14e Tokunoh R. Sodeoka M. Aoe K.-I. Shibasaki M. Tetrahedron Lett. 1995, 36: 8035

Crossref Google Scholar
15a Frost CG. Williams JMJ. Tetrahedron: Asymmetry 1993, 4: 1785

Google Scholar
15b Frost CG. Williams JMJ. Tetrahedron Lett. 1993, 34: 2015

Google Scholar
15c Dawson GJ. Frost CG. Martin CJ. Williams JMJ. Coote SJ. Tetrahedron Lett. 1993, 34: 7793

Google Scholar
15d Chelucci G. Cabras MA. Tetrahedron: Asymmetry 1996, 7: 965

Google Scholar
15e Chelucci G. Berta D. Saba A. Tetrahedron 1997, 53: 3843

Google Scholar
15f Chesney A. Bryce MR. Chubb RWJ. Batsanov AS. Howard JAK. Tetrahedron: Asymmetry 1997, 8: 2337

Google Scholar
16 Morimoto T. Tachibana K. Achiwa K. Synlett 1997, 783

Article in Thieme Connect Google Scholar
17 Boog-Wick K. Pregosin PS. Trabesinger G. Organometallics 1998, 17: 3254

Crossref Google Scholar
18a Allen JV. Coote SJ. Dawson GJ. Frost CG. Martin CJ. Williams JMJ. J. Chem. Soc., Perkin Trans. 1 1994, 2065

Crossref Google Scholar
18b Chesney A. Bryce MR. Tetrahedron: Asymmetry 1996, 7: 3247

Crossref Google Scholar
19 Anderson JC. James DS. Mathias JP. Tetrahedron: Asymmetry 1998, 9: 753

Crossref Google Scholar
20 Rassias GA. Page PCB. Reignier S. Christie SDR. Synlett 2000, 379

Article in Thieme Connect Google Scholar
21 Page PCB. Rassias GA. Bethell D. Schilling MB. J. Org. Chem. 1998, 63: 2774

Crossref Google Scholar
22 Rieche A. Schmitz E. Chem. Ber. 1959, 89: 125

Google Scholar
23 Sprinz J. Kiefer M. Helmchen G. Reggelin M. Huttner G. Walter O. Zsolnai L. Tetrahedron Lett. 1994, 35: 1523

Google Scholar
24 Cesarotti E. Grassi M. Prati L. Demartin F. J. Chem. Soc., Dalton Trans. 1991, 2073

Crossref Google Scholar
25a von Matt P. Lloyd-Jones GC. Minidis ABE. Pfaltz A. Macko L. Neuburger M. Zehnder M. Rüegger H. Pregosin PS. Helv. Chim. Acta 1995, 78: 265

Crossref Google Scholar
25b Steinhagen H. Reggelin M. Helmchen G. Angew. Chem., Int. Ed. Engl. 1997, 36: 2108

Crossref Google Scholar
26 Selvakumar K. Valentini M. Wörle M. Pregosin PS. Albinati A. Organometallics 1999, 18: 1207

Crossref Google Scholar
27 Togni A. Burckhardt U. Gramlich V. Pregosin PS. Salzmann R. J. Am. Chem. Soc. 1996, 118: 1031

Google Scholar
28 Adams H. Anderson JC. Cubbon R. James DS. Mathias JP. J. Org. Chem. 1999, 64: 8256

Crossref Google Scholar
29 Page PCB. Heaney H. Rassias GA. Reignier S. Sampler EP. Talib S. Synlett 2000, 104

Article in Thieme Connect Google Scholar
30a Eschweiler W. Chem. Ber. 1905, 38: 880

Google Scholar
30b Clarke HT. Gillespie HB. Weishans SZ. J. Am. Chem. Soc. 1933, 55: 4571

Google Scholar
30c Icke RN. Moore ML. Org. React. 1945, 5: 31

Google Scholar
30d Wisegarver BB. Alles GA. Org. Synth., Coll. Vol. 3 1955, 723

Google Scholar
31 Ito Y. Sawamura M. Kominami K. Saegusa T. Tetrahedron Lett. 1985, 26: 5303

Crossref Google Scholar
32a Heaney H. Papageorgiou G. Wilkins RF. Tetrahedron 1995, 51: 10737

Crossref Google Scholar
32b Heaney H. Papageorgiou G. Tetrahedron 1996, 52: 3473

Crossref Google Scholar
32c Heaney H. Papageorgiou G. Wilkins RF. Tetrahedron 1997, 53: 2941

Crossref Google Scholar
32d Heaney H. Papageorgiou G. Wilkins RF. Tetrahedron 1997, 53: 14381

Crossref Google Scholar
33a Goodson LH. Christopher H. J. Am. Chem. Soc. 1950, 72: 358

Google Scholar
33b Senkus M. J. Am. Chem. Soc. 1945, 62: 1515

Google Scholar
34a de Sousa SE. O’Brien P. Poumellec P. J. Chem. Soc., Perkin Trans. 1 1998, 1483

Article in Thieme Connect Google Scholar
34b Togni A. Häusel R. Synlett 1990, 633

Article in Thieme Connect Google Scholar
35a Poelert MA. Hulshof LA. Kellogg RM. Recl. Trav. Chim. Pays-Bas 1994, 113: 365

Crossref Google Scholar
35b Dieter RK. Deo N. Lagu B. Dieter J. J. Org. Chem. 1992, 57: 1663

Crossref Google Scholar

36

In these transition state models we have assumed the effect of the sulfur tert-butyl group to be nearly neutral. We believe this to be a reasonable asumption because the S-tert-butyl group would be expected to experience interactions with both the ligand phenyl group and the N-tert-butyl group. It is possible that the sulfur may have considerable sp² character as a result of these interactions; furthermore the S-tert-butyl group would be expected to exert less steric influence over the ligand than does the N-tert-butyl group as a carbon-sulfur bond is normally considerably longer than is a carbon-nitrogen bond.