Development of Palladium-Catalyzed Cycloalkenylation and its Application to Natural Product Synthesis

Masahiro  Toyota; Masataka  Ihara

doi:10.1055/s-2002-32946

ACCOUNT

Development of Palladium-Catalyzed Cycloalkenylation and its Application to Natural Product Synthesis

Masahiro Toyota*, Masataka Ihara*
Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama, Sendai 980-8578, Japan
Fax: +81(22)2176877; e-Mail: matoyota@mail.pharm.tohoku.ac.jp; e-Mail: mihara@mail.pharm.tohoku.ac.jp;

Abstract

All articles of this category

Abstract

To solve the drawback (considerable decrease in yield on a large scale) of cycloalkenylation employing stoichiometric amounts of Pd(OAc)₂, a novel palladium-catalyzed cycloalkenylation has been developed. Stereoselective total syntheses of several bioactive terpenoids have been achieved by means of the above catalytic reaction.

Key words

cycloalkenylation - natural product - catalytic reaction - bioactive terpenoid

Full Text

References

1 Ito Y. Aoyama H. Hirao T. Mochizuki A. Saegusa T. J. Am. Chem. Soc. 1979, 101: 494

2 Kende AS. Roth B. Sanfilippo PJ. Blacklock TJ. J. Am. Chem. Soc. 1982, 104: 5808

3 Kende AS. Sanfilippo PJ. Synth. Commun. 1983, 13: 715

4 Shibasaki M. Mase T. Ikegami S. J. Am. Chem. Soc. 1986, 108: 2090

5 Toyota M. Nishikawa Y. Motoki K. Yoshida N. Fukumoto K. Tetrahedron Lett. 1993, 34: 6099

6 Toyota M. Seishi T. Fukumoto K. Tetrahedron Lett. 1993, 34: 5947

7 Larock RC. Hightower TR. Tetrahedron Lett. 1995, 36: 2423

8 Nozoe S. Furukawa J. Sankawa U. Shibata S. Tetrahedron Lett. 1976, 195

9 Nakamura H. Takita T. Umezawa H. Kunishita M. Nakayama Y. Itaya Y. J. Antibiot. 1974, 27: 301

10 Mehta G. Srikrishna A. Chem. Rev. 1997, 97: 671

11 Stevens KE. Paquette LA. Tetrahedron Lett. 1981, 22: 4393

12 Manchand PS. White DJ. Wright H. Clardy J. J. Am. Chem. Soc. 1973, 95: 2705

13 Toyota M. Ihara M. Tetrahedron 1999, 40: 1551

14 Toyota M. Seishi T. Yokoyama M. Fukumoto K. Kabuto C. Tetrahedron Lett. 1992, 33: 4581

15 Piers E. Abeysekera BF. Herbert DJ. Suckling ID. Can. J. Chem. 1985, 63: 3418

16 Toyota M. Majo VJ. Ihara M. Tetrahedron Lett. 2001, 42: 1555

17 Dabrah TT. Harwood HL. Huang LG. Jankovich ND. Kaneko T. Li J.-C. Lindsey S. Moshier PM. Subashi TA. Therrien M. Watts PC. J. Antibiot. 1997, 50: 1

18 Wani MC. Taylor ME. Coggon P. McPhail AT. J. Am. Chem. Soc. 1971, 93: 2325

19 Stratmann K. Burgoyne DL. Moore RE. Patterson GML. Smith CD. J. Org. Chem. 1994, 59: 7219

20 To oxidize Pd(0) produced by reductive elimination p-benzoquinone might be useful: Ito Y. Hirao T. Saegusa T. J. Org. Chem. 1978, 43: 1011 ; however a reproducible palladium-catalyzed cycloalkenylation has never been found so far

21 Cross BE. Norton K. J. Chem. Soc. 1965, 1570

22 Brundret KM. Dalziel W. Hesp B. Jarvis JAJ. Neidle SJ. J. Chem. Soc., Chem. Commun. 1972, 1027

23 Majima R. Suginome H. Morio S. Ber. 1924, 57: 1456

The silyl enol ether 42 was prepared from 38 by conjugate reduction followed by silylation.

24a Toyota M. Wada T. Nishikawa Y. Yanai K. Fukumoto K. Synlett 1994, 597

24b Toyota M. Wada T. Nishikawa Y. Yanai K. Fukumoto K. Kabuto C. Tetrahedron 1995, 51: 6927

25 Kende AS. Roth B. Sanfilippo PJ. J. Am. Chem. Soc. 1982, 104: 1784

26 Larock RC. Lee NH. Tetrahedron Lett. 1991, 32: 5911

27 Hegedus L. In Comprehensive Organometallic Chemistry II Vol. 12: Abel EW. Stone FGA. Wilkinson G. Pergamon Press; New York: 1997.

28 Lyons EJ. In Oxygen Complexes and Oxygen Activation by Transition Metals Martell AE. Sawyer DT. Plenum Press; New York: 1988. p.233-251

29 For a recent review: Mander LN. Chem. Rev. 1992, 92: 573

30 Toyota M. Odashima T. Wada T. Ihara M. J. Am. Chem. Soc. 2000, 122: 9036

31 Horiguchi Y. Matsuzawa S. Nakamura E. Kuwajima I. Tetrahedron Lett. 1986, 27: 4025

32 Parikh JR. von Doering WE. J. Am. Chem. Soc. 1967, 89: 5505

33 Wadsworth WS. Emmons WD. J. Am. Chem. Soc. 1961, 83: 1733

34 Faria V. Krishnamurthy V. Scott WJ. Org. React. 1997, 50: 1

35 Wilds AL. Org. React. 1944, 2: 178

36a Toyota M. Yokota M. Ihara M. J. Am. Chem. Soc. 2001, 123: 1856

36b Toyota M. Yokota M. Ihara M. Org. Lett. 1999, 1: 1627

36c Toyota M. Yokota M. Ihara M. Tetrahedron Lett. 1999, 40: 1551

37 Wenkert E. Chem. Ind. (London) 1955, 282

38 Toyota M. Wada T. Fukumoto K. Ihara M. J. Am. Chem. Soc. 1998, 120: 4916

39 Nace HR. Org. React. 1962, 12: 57

40 d’Angelo JD. Desmaele D. Dumas F. Guingant A. Tetrahedron: Asymmetry 1992, 3: 459

41 Toyota M. Wada T. Ihara M. J. Org. Chem. 2000, 65: 4565

42 Toyota M. Rudyanto M. Ihara M. Tetrahedron Lett. 2000, 41: 8929