Strategies for the Preparation of Differentially Protected ortho-Prenylated Phenols

Christophe Hoarau; Thomas R. R. Pettus

doi:10.1055/s-2003-36234

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Strategies for the Preparation of Differentially Protected ortho-Prenylated Phenols

Christophe Hoarau, Thomas R. R. Pettus*^a
Department of Chemistry and Biochemistry, University of California at Santa Barbara, Santa Barbara, California 93106, USA
Fax: +1(805)8935690; e-Mail: pettus@chem.ucsb.edu;

Abstract

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Abstract

A new process for ortho-prenylation of phenols is presented within the context of known methods. All of the processes are briefly assessed with regards to the substitution patterns and accompanying functional groups tolerated by each strategy. The conclusion reached is that a new procedure using ortho-quinone methides, for which an experimental protocol is provided, offers the greatest generality and flexibility in the preparation of ortho-prenylated phenol derivatives.

1 Introduction
2 Desymmetrization of Dihydroxy Aromatics
3 Directed ortho-Metalation (DoM) and Alkylation
4 Metal-Halogen Exchange and Metal-Mediated Coupling
5 Phenoxide ortho-C-Alkylation
6 Claisen Rearrangement
7 Friedel-Crafts-like Prenylations
8 Birch Reduction of 2,2-Dimethyl-2H-chromenes
9 Net Conjugate Addition to para-Quinone
10 Benzylic Couplings
11 Conclusions

Key words

prenylation - phenols - ortho-alkylation - ortho-methide

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References

1 Brandt U. Biofactors 1999, 9: 95

2 Fukui H. Feroj Hassan AFM. Ueoka T. Kyo M. Phytochemistry 1998, 47: 1037

3 Mori K. Waku M. Sakakibara M. Tetrahedron 1985, 41: 2825

4a Basset C. Sherwood RT. Kepler JA. Hamilton PB. Phytopathology 1967, 57: 1046

4b Wächter GA. Hoffmann JJ. Furbacher T. Blake ME. Timmermann BN. Phytochemistry 1999, 52: 1469

5 Ghirtis K. Pouli N. Marakos P. Skaltsounis A.-L. Leonce S. Caignard DH. Atassi G. Heterocycles 2000, 53: 93

6 Meragelman KM. McKee TC. Boyd MR. J. Nat. Prod. 2001, 64: 546

7a Kang SY. Lee KY. Sung SH. Park MJ. Kim YC. J. Nat. Prod. 2001, 64: 683

7b Carney JR. Krenisky JM. Williamson RT. Luo J. J. Nat. Prod. 2001, 64: 203

7c Verotta L. Appendino G. Beelloro E. Bianchi F. Sterner O. Lovati M. Bombardelli E. J. Nat. Prod. 2002, 65: 433

8 Nicolaou KC. Pfefferkorn JA. Roecker AJ. Cao G.-Q. Barluenga S. Mitchell HJ. J. Am. Chem. Soc. 2000, 122: 9939

9 Wang Y. Tan W. Li WZ. Li Y. J. Nat. Prod. 2001, 64: 196

10a Snieckus V. Chem. Rev. 1990, 90: 879

10b Snieckus V. Sibi MP. J. Org. Chem. 1983, 48: 1937

10c Metallinos C. Nerdinger S. Snieckus V. Org. Lett. 1999, 1: 1183

10d Ronald RC. Winkle MR. J. Org. Chem. 1982, 47: 2101

11 Mechoulam R. Gaoni Y. J. Am. Chem. Soc. 1965, 87: 3273

12 Kirschleger B. Bouzbouz S. Synthesis 1994, 714

13a Simas ABC. Coelho AL. Costa PRR. Synthesis 1999, 1017

13b Fitton AO. Ramage GR. J. Chem. Soc. 1962, 4870

14a Bieber LW. Chiappeta ADA. De Moraes E. Souza MA. Generino RM. Rolim Neto P. J. Nat. Prod. 1990, 53: 706

14b Anderson EL. Parham WE. J. Am. Chem. Soc. 1948, 70: 4187

15a Jung Y.-S. Joe B.-Y. Seong C.-M. Park N.-S. Bull. Korean Chem. Soc. 2000, 21: 463

15b Depew KM. Danishefsky SJ. Rosen N. Sepp-Lorenzino L. J. Am. Chem. Soc. 1996, 118: 12463

16a Tsukayama M. Kikuchi M. Kawamura Y. Heterocycles 1994, 38: 1487

16b Tsukayama M. Kikuchi M. Kawamura Y. Chem. Lett. 1994, 1203

16c Kim YH. Yang SG. Tetrahedron Lett. 1999, 40: 6051

17a Beckwith ALJ. Gara WB. J. Chem. Soc., Perkin Trans. 2 1975, 795

17b Ballester P. Capo M. Saa JM. Tetrahedron Lett. 1990, 31: 1339

17c Garcias X. Ballester P. Capo M. Saa JM. J. Org. Chem. 1994, 59: 5093

17d Weinstock J. Ladd DL. Wilson JM. Brush CK. Yim NCF. Gallagher G. McCarthy ME. Silvestry J. Sarau HM. Flaim KE. Ackerman DM. Setler PE. Tobia AJ. Hahn RA. J. Med. Chem. 1986, 29: 2315

18 Barluenga J. Sanz R. Fañanás FJ. Tetrahedron Lett. 1997, 6103

For examples of this procedure, see:

19a Kuhnke J. Bohlmann F. Tetrahedron Lett. 1985, 26: 3955

19b Chen KM. Semple JE. Joullie MM. J. Org. Chem. 1985, 50: 3997

19c Le Noble WJ. Synthesis 1970, 1

19d De Bernardi M. Vidari G. Vita Finzi P. Fronza G. Tetrahedron 1992, 48: 7331 ; observes 31% of C-prenylated product of 4-methoxyphenol. Note, if O-prenylation occurs, the subsequent Claisen rearrangement leads to a reverse prenyl residue

19e Yamada S. Ono F. Katagiri T. Tanaka J. Synth. Comm. 1975, 5: 181

19f Fürstner A. Gastner T. Org. Lett. 2000, 2467

19g Yamada S. Futara O. Katagiri T. Tanaka J. Bull. Chem. Soc. Jpn. 1977, 50: 750

19h Glüsenkamp K.-H. Büchi G. J. Org. Chem. 1986, 51: 4481

19i Casiraghi G. Bigi F. Sartori G. Synthesis 1981, 310

19j Toyoda T. Sasakura K. Sugasawa T. J. Org. Chem. 1981, 46: 189

19k Piccolo O. Filippini L. Tinucci L. Valoti E. Cittero A. Tetrahedron 1986, 42: 885

20a Hlubucek J. Ritche E. Taylor WC. Tetrahedron Lett. 1969, 1369

20b Pettus TRR. Inoue M. Chen X.-T. Danishefsky SJ. J. Am. Chem. Soc. 2000, 122: 6160

20c Pernin R. Muyard F. Bevalot F. Tillequin F. Vaquette J. J. Nat. Prod. 2000, 63: 245

20d Monteiro N. Arnold A. Balme G. Synlett 1998, 1111

20e Bell D. Davies MR. Geen GR. Mann IS. Synthesis 1995, 707

20f Li J. Nicolaou KC. Angew. Chem. Int. Ed. 2001, 40: 4264

21 Iikubo K. Ishikawa Y. Ando N. Umezawa K. Nishiyama S. Tetrahedron Lett. 2002, 43: 291

22a Pochini A. Marchelli R. Bocchi V. Gazz. Chim. Ital. 1975, 105: 1245

22b Pochini A. Marchelli R. Bocchi V. Gazz. Chim. Ital. 1975, 105: 1253

22c Jain AC. Prasad AK. Indian J. Chem., Sect. B 1990, 29: 525

22d Sudalai A. Rao GSK. Indian J. Chem., Sect. B 1989, 28: 760

22e Bigi F. Carloni S. Maggi R. Muchetti C. Rastelli M. Sartori G. Synthesis 1998, 301

22f Dieter JW. Li Z. Nicholas KM. Tetrahedron Lett. 1987, 28: 5415

22g De Renzi A. Panunzi A. Saporito A. Vitagliano A. J. Chem. Soc., Perkin Trans. 2 1983, 993

22h De Felice V. De Renzi A. Funicello M. Panuzi A. Saporito A. Gazz. Chim. Ital. 1985, 115: 13

22i Narasaka K. Bald E. Mukaiyama T. Chem. Lett. 1975, 1041

22j Dauben WG. Cogen JM. Behar V. Tetrahedron Lett. 1990, 31: 3241

22k Corey EJ. Wu LI. J. Am. Chem. Soc. 1993, 115: 9327

23a Bissada S. Lau CK. Bernstein MA. Dufresne C. Can. J. Chem. 1994, 72: 1866

23b Chauder BA. Lopes CC. Lopes RSC. Da Silva AJM. Snieckus V. Synthesis 1998, 279

For the reduction of chromenes, see:

24a Aniol M. Wawrzenczyk C. Heterocycles 1994, 38: 2655

24b Birch AJ. Maung M. Pelter AJ. Aust. J. Chem. 1969, 22: 1923

24c Chauder BA. Kalinin AV. Snieckus V. Synthesis 2001, 140

25 Silane: Hagiwara E. Hatanaka Y. Gohda K.-I. Hiyama T. Tetrahedron Lett. 1995, 36: 2773

Tin:

26a Maruyama K. Naruta Y. J. Org. Chem. 1978, 43: 3796

26b Naruta Y. J. Org. Chem. 1980, 45: 4097

26c Takuwa A. Soga O. Mishima T. J. Org. Chem. 1987, 52: 1261

26d Naruta Y. Maruyama K. Org. Synth. 1992, 71: 125

27 Indium: Akari S. Katsumura N. Butsugan Y.
J. Organomet. Chem. 1991, 415: 7

π-Allylnickel complex:

28a Hegedus LS. Waterman EL. Catlin J. J. Am. Chem. Soc. 1972, 94: 7155

28b Hegedus LS. Evans BR. J. Am. Chem. Soc. 1978, 100: 3461

29a Negishi E.-T. Matsushita H. Okukado N. Tetrahedron Lett. 1981, 22: 2715

29b Lipshutz BH. Bulow G. Fernandez-Lazaro F. Kim S.-K. Lowe R. Mollard P. Stevens KL. J. Am. Chem. Soc. 1999, 121: 11664

29c Lipshutz BH. Bulow G. Lowe R. Stevens KL. J. Am. Chem. Soc. 1996, 118: 5512

29d Srogl J. Allred GD. Liebeskind LS. J. Am. Chem. Soc. 1997, 119: 12376

29e Zhang S. Marshall D. Liebeskind LS. J. Org. Chem. 1999, 64: 2796

30a Van De Water RW. Magdziak DJ. Chau JN. Pettus TRR. J. Am. Chem. Soc. 2000, 122: 6502

30b Jones RM. Van De Water RW. Lindsey CC. Hoarau C. Ung T. Pettus TRR. J. Org. Chem. 2001, 66: 3435

30c Lindsey CC. Gómez-Días C. Villalba JM. Pettus TRR. Tetrahedron 2002, 58: 4559

31 The 2,6-dihydroxybenzaldehyde 88 was prepared from the demethylation of 2,6-dimethoxybenzaldehyde in 58% following reported literature procedure: Boulos Z. Attardo G. Barriault N. Penney C. J. Chem. Soc., Perkin Trans. 1 1997, 2925

32

The lability of the remaining OBOC residue in 92 and our inability to purify this substance is believed to be responsible for the reduced yield of 97 when compared with the overall yields of 95, 96 and 98.