A Formal Synthesis of Ionomycin
Featuring a Permanganate-Mediated Oxidative Cyclisation

Yingfa Li; John P. Cooksey; Zhanghua Gao; Philip J. Kocieński; Stephen M. McAteer; Thomas N. Snaddon

doi:10.1055/s-0030-1258327

PAPER

A Formal Synthesis of Ionomycin Featuring a Permanganate-Mediated Oxidative Cyclisation

Yingfa Li, John P. Cooksey, Zhanghua Gao, Philip J. Kocieński*, Stephen M. McAteer, Thomas N. Snaddon
The School of Chemistry and the Institute of Process Research and Development, Leeds University, Leeds LS2 9JT, UK
Fax: +44(113)3436401; e-Mail: p.j.kocienski@leeds.ac.uk;

Abstract

All articles of this category

Abstract

Key steps in a synthesis of the C17-C32 fragment of ionomycin are (a) an auxiliary-directed oxidative cyclisation of a diene with potassium permanganate to construct a tetrahydrofuran ring and four stereogenic centres in a single operation, and (b) a chain-appendage reaction featuring the alkylation of an enolsilane by an oxocarbenium ion generated from a 2-phenylsulfonyl-substituted tetrahydrofuran.

Key words

ionomycin - permanganate oxidation - directed reduction - crotylboration - carbocupration

Full Text

References

1 Liu C. Hermann TE. J. Biol. Chem. 1978, 253: 5892

2 Liu W.-C. Slusarchyk DS. Astle G. Trejo WH. Brown WE. Meyers E. J. Antibiot. 1978, 31: 815

3 Toeplitz BK. Cohen AI. Funke PT. Parker WL. Gougoutas JZ. J. Am. Chem. Soc. 1979, 101: 3344

4 Erdahl WL. Chapman CJ. Taylor RW. Pfeiffer DR. J. Biol. Chem. 2000, 275: 7071

5 Gao Z. Li Y. Cooksey JP. Snaddon TN. Schunk S. Viseux EME. McAteer SM. Kocieński PJ. Angew. Chem. Int. Ed. 2009, 48: 5022

6 Evans DA. Dow RL. Shih TL. Takacs JM. Zahler R. J. Am. Chem. Soc. 1990, 112: 5290

7 Hanessian S. Cooke NG. Dehoff B. Sakito Y. J. Am. Chem. Soc. 1990, 112: 5276

8 A third total synthesis of ionomycin was reported by Lautens and co-workers in 2002, see: Lautens M. Colucci JT. Hiebert S. Smith ND. Bouchan G. Org. Lett. 2002, 4: 1879

9 For an excellent review of the oxidation of dienes and polyenes mediated by transition-metal-oxo species, see: Piccialli V. Synthesis 2007, 2585

10 Burke SD. Cobb JE. Takeuchi K. J. Org. Chem. 1990, 55: 2183

11 Roush WR. Ando K. Powers DB. Palkowitz AD. Halterman RL. J. Am. Chem. Soc. 1990, 112: 6339

12 Roush WR. Palkowitz AD. Ando K. J. Am. Chem. Soc. 1990, 112: 6348

13 Scheidt KA. Bannister TD. Tasaka A. Wendt MD. Savall BM. Fegley GJ. Roush WR. J. Am. Chem. Soc. 2002, 124: 6981

14 Brown HC. Bhat KS. Randad RS. J. Org. Chem. 1989, 54: 1570

15 Brown HC. Bhat KS. J. Am. Chem. Soc. 1986, 108: 5919

16 Smith AB. Cho YS. Friestad GK. Tetrahedron Lett. 1998, 39: 8765

17 Kocieński PJ. Brown RCD. Pommier A. Procter M. Schmidt B. J. Chem. Soc., Perkin Trans. 1 1998, 9

18 Corey EJ. Katzenellenbogen JA. J. Am. Chem. Soc. 1969, 91: 1851

19 Nilsson K. Andersson T. Ullenius C. Gerold A. Krause N. Chem. Eur. J. 1998, 4: 2051

20 Ghosez L. Haveaux B. Viehe HG. Angew. Chem. Int. Ed. Engl. 1969, 8: 454

21 Haveaux B. Dekoker A. Rens M. Sidani AR. Toye J. Ghosez L. Org. Synth., Coll. Vol. VI 1988, 282

22 Walba DM. Przybyla CA. Walker CB. J. Am. Chem. Soc. 1990, 112: 5624

23 Cecil ARL. Brown RCD. Org. Lett. 2002, 4: 3715

24 Cecil ARL. Brown RCD. Tetrahedron Lett. 2004, 45: 7269

25 Cecil ARL. Hu YL. Vicent MJ. Duncan R. Brown RCD. J. Org. Chem. 2004, 69: 3368

26 Head GD. Whittingham WG. Brown RCD. Synlett 2004, 1437

27 Hu YL. Brown RCD. Chem. Commun. 2005, 5636

28 Brown LJ. Spurr IB. Kemp SC. Camp NP. Gibson KR. Brown RCD. Org. Lett. 2008, 10: 2489

29 Bhunnoo RA. Hobbs H. Laine DI. Light ME. Brown RCD. Org. Biomol. Chem. 2009, 7: 1017

30

The relative and absolute stereochemistry of the lactone 21 was established by a single crystal X-ray analysis of its enantiomer prepared by an analogous route. See the electronic Supporting Information for details

31 Russell ST. Robinson JA. Williams DJ. J. Chem. Soc., Chem. Commun. 1987, 351

32 Ley SV. Lygo B. Wonnacott A. Tetrahedron Lett. 1985, 26: 535

33 Deslongchamps P. Atlani P. Fréhel D. Malaval A. Moreau C. Can. J. Chem. 1974, 52: 3651

34 Deslongchamps P. Atlani P. Fréhel D. Moreau C. Can. J. Chem. 1972, 50: 3402

35 Deslongchamps P. Moreau C. Can. J. Chem. 1971, 49: 2465

36 Deslongchamps P. Moreau C. Fréhel D. Chěnevert R. Can. J. Chem. 1975, 53: 1204

37 Taillefer RJ. Thomas SE. Nadeau Y. Beierbeck H. Can. J. Chem. 1979, 57: 3041

38 Taillefer RJ. Thomas SE. Nadeau Y. Fliszár S. Henry H. Can. J. Chem. 1980, 58: 1138

39 Brown DS. Bruno M. Davenport RJ. Ley SV. Tetrahedron 1989, 45: 4293

40 Evans DA. Allison BD. Yang MG. Masse CE. J. Am. Chem. Soc. 2001, 123: 10840

41 Rychnovsky SD. Rogers B. Yang G. J. Org. Chem. 1993, 58: 3511

42 Schmitt A. Reissig H.-U. Synlett 1990, 40

43 Schmitt A. Reissig H.-U. Eur. J. Org. Chem. 2000, 3893

44 Schmitt A. Reissig H.-U. Eur. J. Org. Chem. 2001, 1169

45 Larsen CH. Ridgway BH. Shaw JT. Woerpel KA. J. Am. Chem. Soc. 1999, 121: 12208

46 Brown RCD. Bataille CJ. Hughes RM. Kenney A. Luker TJ. J. Org. Chem. 2002, 67: 8079

47 Brown RCD. Hughes RM. Keily J. Kenney A. Chem. Commun. 2000, 1735

48 Morris CL. Hu YL. Head GD. Brown LJ. Whittingham WG. Brown RCD. J. Org. Chem. 2009, 74: 981

49 Brown RCD. Keily JF. Angew. Chem. Int. Ed. 2001, 40: 4496

50 Fürstner A. Aïssa C. Riveiros R. Ragot J. Angew. Chem. Int. Ed. 2002, 41: 4763

Supplementary Material

Supporting Information

Primary Data

Primary Data