Abstract
The reaction of cyclic orthoesters of cyclohexanes and steroides with trimethylsilylchloride,-azide and-cyanide points out novel, mechanistic aspects as well as remarkable preparative possibilities. The mixture1 a/1 b of theexo/endo stereoisomers of the cyclic orthoesters derived fromcis-cyclohexane-1,2-diol was transformed to the expected 1-yl-ethanoate3 of thetrans-2-chlorocyclohexan-1-ol. In contrast the reaction of1 a/1 b with trimethylsilylazide and trimethylsilycyanide yields the correspondingexo/endo mixtures of2 a/2 b and2 c/2 d resp. The cyclic orthoester oftrans-cyclohexan-1,2-diol (4) similarily affords the products5 a and5 b, whereas transformation with trimethylsilylchloride 1-yl-ethanoate of thecis-2-chlorocyclohexan-1-ol could not be achieved for steric reasons. The cyclic orthoesters6 a/6 b ofcis-cyclohex-1-en-3,4-diol are converted regio- and stereospecifically to the products7 and9 using trimethylsilychloride and- azide, whereas theexo/endo mixture8 a/8 b of the corresponding cyclic orthoester derivative is formed with trimethylsilylcyanide. The orthoesters10 a/10 b prepared from 2,3-cis-dihydroxycyclohexanone-1 give thetrans-2-chloro-3-oxocyclohexyl-ethanoate (11) and its elimination product12. In analogy13 is produced by treating10 a/10 b with trimethylsilylacetate. Theexo/endo mixture of cyclic esters14 a/14 b 3α-cholestan-2α,3α-diol gives the corresponding mixture15 a/15 b when treated with trimethylsilycyanide. Reaction of Trimethylsilychloride with14 a/14 b affords mainly thetrans-diequatorial product17 a and only small amounts of thetrans-diaxial product17b. In contrast the mixture18a/18b yields exclusively thetrans-diaxials product20 on reaction with trimethylsilylchloride. With trimethylsilcyanide the cyclic orthoester derivative21 a/21 b is formed. The cyclic esters22 a/22 b of 1α,2α-dihydroxychloestanone-3 react with trimethylsilylchloride to give the easily explicable elimination product23 and the rearranged 3-methoxy-cholesten-3-one-2 (24). The corresponding cyclic orthesters25 a/25 b of 1α,2α-dihydroxy-3-oxo-androstans-17β-yl-ethanoate in a similar way afford the elimination product26 to a small extent and the rearranged 3-methoxy-2-oxo-androstan-17β-yl-ethanoate (27) as the main product.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Literatur
R. H. De Wolfe, Carboxylic Ortho Acid Derivatives. New York-London: Academic Press 1970.
K. Kondo, M. Matsumoto, undF. Mori, Angew. Chem.87, 109 (1975).
W. S. Johnson, L. Werthemann, W. R. Bartlett, T. J. Brcksom, Tsung-Tee Li, D. J. Faulkner undM. R. Peterson, J. Amer. Chem. Soc.92, 741 und 4463 (1970).
P. N. Confalone, G. Pizzolato, E. G. Baggiolini, D. Dollar undM. R. Uskokovic, J. Amer. Chem. Soc.97, 5936 (1975).
F. Wiesner, Adv. Org. Chem. Vol. 8, S. 295. New York-Sydney-Toronto: Wiley Intersience Publishers. 1972.
T. Goto, Y. Kishi, S. Takahashi undY. Hirata, Tetrahedron21, 2059 (1965).
K. B. Wiberg undK. A. Saegebarth, J. Amer. Chem. Soc.79, 6256 (1957).
P. Deslongchamps, Tetrahedron31, 2463 (1975).
J.-M. Lehn undG. Wipff, Helv. Chim. Acta61, 1274 (1978).
D. A. Evans, G. L. Carroll undL. K. Truesdale, J. Org. Chem.39, 914 (1974).
D. A. Evans, L. K. Truesdale, K. G. Grimm undS. L. Nesbitt, J. Amer. Chem. Soc.99, 5009 (1977).
M. S. Newman undD. R. Olson, J. Org. Chem.38, 4203 (1973).
R. U. Lemieux undC. Altona, Topics Stereochem.4, 39 (1969).
G. A. Jeffrey, J. A. Pople undL. Radom, Carbohydr. Res.25, 117 (1972).
S. David, O. Eisenstein, W. J. Hehre, L. Salem undR. Hoffmann, J. Amer. Chem. Soc.95, 3806 (1973).
J. Fleming, The Frontier Orbitals and Organic Chemical Reactions. London-New York: John Wiley & Sons 1976.
N. D. Epiotis, W. R. Cherry, S. Shhik, R. Y. Yates undF. Bernardi, in: Topics in Current Chemistry, Structural Theory of Organic Chemistry. Berlin-Heidelberg-New York: Springer. 1977.
C. A. Grob, Angew. Chem.1961, S. 758, ibid. Angew. Chem.1965, S. 459, ibid. Angew. Chem.1967, S.1.
C. A. Grob, Adv. Org. Chem.8, 227 (1972).
K. B. Becker undC. a. Grob, in: The Chemistry of functional groups, Supplement A, The chemistry of double-bonded functional groups, Part 2 (S. Patai). London-New York-Sydney-Toronto: Wiley & Sons. 1977.
R. U. Lemieux, Can. J. Chem.43, 2199 (1965).
M. S. Newman undChin H. Chen, J. Amer. Chem. Soc.95, 278 (1973).
M. S. Newman, undChin H. Chen, J. Org. Chem.38, 1173 (1973).
Siehe lit. cit.
K. Freudenberg undH. Scholz, Chem.Ber.63, 1969 (1930).
G. Briegleb, Elektronen-Donator-Acceptor-Komplexe, S. 54. Berlin-Heidelberg-New York: Springer. 1961.
S. Hünig, Angew. Chem.76, 400 (1964).
H. Paulsen, Z. Györgydeak undM. Friedemann, Chem. Ber.107, 1568 (1974).
N. Micheel, Adv. Carbohydr. Chem.16, 85, (1961).
J. I. Shaw undR. Stevenson, J. Chem. Soc.1955, 3539.
H. S. Ringold, E. Batres, O. Mancera undG. Rosenkranz, J. Org. Chem.21, 1432 (1959).
Siehe lit. cit., S. 116.
D. H. R. Barton undJ. F. King, J. Chem. Soc.1958, 4398.
R. Altona, Rec. Trav. Chim. Pays-Bas82, 1080 (1963).
E. Buncel undJ. P. Millington, Can. J. Chem.43, 547 (1965).
A. Fischer, Dissertation Univ. Basel1961.
R. Keese undV. Rasetti, Univ. Bern, private Mitt.
O. Eisenstein, Nguyen Trong Anh, Y. Jean, A. Devaquet, J. Chantacuzene undL. Salem, Tetrahedron30, 1717 (1974).
A. Fürst undP. A. Plattner, Abstracts Papers 12th International Congress of Pure and Applied Chemistry, S. 409, New York, 1951.
T. Goto, J. Amer. Chem. Soc.83, 251 (1961).
L. T. Fieser undH. A. Fieser, Stereoide, S. 641 ff. Weinheim: Verlag Chemie. 1961.
D. N. Kirk undM. P. Hartshorn, Reaction Mechanisms in Organic Chemistry, Stereoid Reaction Mechanisms, Monograph 7. Amsterdam-London-New York-Princeton: Elsevier Publishing Company. 1968.
B. Ellis undV. Petrow, J. Chem. Soc.1953, 3869.
C. W. Shoppee undS. C. Sharma, J. Chem. Soc. C,1967, 2385.
W. Reusch undR. LeMahieu, J. Org. Chem.28, 2443 (1963).
M. F. Clarke undL. N. Owen, J. Chem. Soc.1949, 318.
M. F. Clarke, Organic Synthesis Vol.3, S. 217.
H. Z. Sable, Tetrahedron26, 1509 (1970).
H. Gmelin, Handbuch der Anorganischen Chemie, Mangan Teil C 2. Verlag Chemie.
L. Mangoni, Tetrahedron Lett.45, 4485 (1973).
J. Greenberg undJ. G. Moffat, J. Amer. Chem. Soc.95, 4016 (1973).
D. H. R. Barton undH. Alt, J. Chem. Soc.,1954, 4284.
J. F. King undA. D. Allbutt, Can. J. Chem.48, 1754 (1970).
Author information
Authors and Affiliations
Additional information
Herrn Prof. Dr.H. Pommer mit den besten Wünschen zum 60. Geburtstag gewidmet.
Rights and permissions
About this article
Cite this article
Becsi, F., Zbiral, E. Zum Verhalten von Orthocarbonsäureestern gegenüber Trimethylsilylchlorid, -azid und -cyanid. Monatshefte für Chemie 110, 955–978 (1979). https://doi.org/10.1007/BF00906692
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF00906692