Trans Dialkoxylation of Cyclic Alkenes: A Prévost-Type Reaction

Abstract

Reaction of anhydrous silver perchlorate, sym-collidine, and iodine (2:1:1 molar ratio) with cyclic alkenes and an excess of an alcohol in CH₂Cl₂ affords trans-1,2-dialkoxycycloalkanes in high yields and purity. The reaction occurs via initial formation of the trans-iodoethers, which undergo Ag-assisted iodide abstraction to give the trans-diethers.

alkenes - iodoalkoxylation - dialkoxylation - silver perchlorate - collidine

References

1

Professor Emeritus, Villanova University, Villanova, PA 19085, USA.

2

Ph.D., Villanova University, 1992. Current address: Quaker Chemical Corp., Conshohocken, PA 19428, USA.

3

M.S., Villanova University, 1987. Current address: Bristol-Myers Squibb Pharmaceutical Research Institute, Princeton, NJ 08540, USA.

4

M.S., Ph.D., Villanova University, 1983, 1986. Current address: Quaker Chemical Corp., Conshohocken, PA 19428, USA.

5 Iodofluorination of alkenes using AgBF₄, I₂: Evans RD. Schauble JH. Synthesis  1987,  551 

6a Pocker Y. Kevill DN. J. Am. Chem. Soc.  1965,  87:  5060 

6b Kevill DN. Suthoff RF. J. Chem. Soc., Perkin Trans. 2  1977,  201 

7 Reviewed by: Kevill DN. In The Chemistry of Halides, Pseudo-halides and Azides, Part 2   Patai S. Rappoport Z. John Wiley and Sons; New York: 1983.  p.933 

8 Vona JA. Steigman J. J. Am. Chem. Soc.  1959,  81:  1095 

9a Peard WJ. Pflaum RT. J. Am. Chem. Soc.  1958,  80:  1593 

9b Bando Y. Nagakura S. Theor. Chim. Acta  1968,  9:  210 

9c Molina M. Tabak S. J. Inorg. Nucl. Chem.  1972,  34:  2985 

Reviews on N-iodonium complexes:

10a Varvoglis A. The Organic Chemistry of Polycoordinated Iodine   VCH Publishers, Inc.; New York: 1992.  p.355 

10b Moeller T. Inorganic Chemistry   John Wiley and Sons, Inc.; New York: 1952.  p.460 

11 Roberts JD. J. Org. Chem.  1979,  44:  2658 

12 Crist DR. Hsieh Z.-H. Jordan GJ. Schinco FP. Maciorowski CA. J. Am. Chem. Soc.  1974,  96:  4932 

13 Crookes JV. Woolf AA. J. Chem. Soc., Dalton Trans.  1973,  1241 

14 Likewise, Prévost reactions of trisubstituted alkenes give very low yields of diols, plus allylic alcohols and ketones: Parrilli M. Dovinola V. Mangoni L. Gazz. Chim. Ital.  1974,  104:  829 

15a Rickborn B. Gerkin RM. J. Am. Chem. Soc.  1968,  90:  4193 

15b Bhatia KA. Eash KJ. Leonard NM. Oswald MC. Mohan RS. Tetrahedron Lett.  2001,  42:  8129 

16a Davidson RI. Kropp PJ. J. Org. Chem.  1982,  47:  1904 

16b

Iodoether 14 was previously obtained by reaction of norbornene with silver oxide, I₂ in MeOH.

17 Jarret RM. Veniero JC. Byrne TP. Saunders M. Laidig KE. J. Am. Chem. Soc.  1988,  110:  8287 

Analogous replacement of the 3-exo-iodo group by 3-exo-acetoxyl has been reported:

18a Cambie RC. Lindsay BG. Rutledge PS. Woodgate PD. J. Chem. Soc., Perkin Trans. 1  1976,  845 

18b Cambie RC. Hayward RC. Lindsay BG. Phan AIT. Rutledge PS. Woodgate PD. J. Chem. Soc., Perkin Trans. 1  1976,  1961 

19 Lemieux RU. Fraser-Reid B. Can J. Chem.  1965,  43:  1460 

20 Sweet F. Brown RK. Can. J. Chem.  1966,  44:  1571 

21 Silverstein RM. Webster FX. Spectrometric Identification of Organic Compounds   6th ed.:  John Wiley & Sons, Inc.; New York: 1998.  p.222 

22 Johnson WS. Bauer VJ. Margrave JL. Frisch MA. Dreger LH. Hubbard WN. J. Am. Chem. Soc.  1961,  83:  606 

23 Brinkley SR. J. Am. Chem. Soc.  1940,  62:  3524 

24 Smith GF. Ring F. J. Am. Chem. Soc.  1937,  59:  1889 

25 Cambie RC. Hayward RC. Roberts JL. Rutledge PS. J. Chem. Soc., Perkin Trans. 1  1974,  1858 

26 Lemieux RU. Morgan AR. Can. J. Chem.  1965,  2190 

27 Barluenga J. Alonso-Cires L. Campos PJ. Asensio G. Tetrahedron  1984,  40:  2563 

28 Uemura S. Fukuzawa S. J. Chem. Soc., Perkin Trans. 1  1985,  471 

29 Grützmacher H.-F. Fechner K.-H. Org. Mass Spectrom.  1973,  7:  573 

30 Tvaroska I. Carver JP. Theochem.  1997,  395:  1