Synthesis of medium ring ethers. Part 3. Disproof of the proposed 2,8-disubstituted oxocane structure for gloeosporone. Synthesis of pseudo-gloeosporone

Synthesis of the cis- and trans-2,8-disubstituted oxocane derivatives 2 and 3(carrying the unusual γ,δ-diketohexanecarboxylic acid side chain) by ozonolysis of the alkynes 14 and 18(prepared respectively from the alcohols 11 and 15) demonstrated unequivocally that neither of these compounds nor their hydroxy-γ-lactone ring (lactol) tautomers 1 corresponded to the naturally occurring fungal self germination inhibitor gloeosporone. A study of 4,5-dioxohexanoic itself 9 revealed a remarkably low tendency to exist as its hydroxy-γ-lactone (lactol) tautomer 10.

[1]  M. Fitzgibbon,et al.  Solution structure of the major binding protein for the immunosuppressant FK506 , 1991, Nature.

[2]  R F Standaert,et al.  Atomic structure of FKBP-FK506, an immunophilin-immunosuppressant complex , 1991, Science.

[3]  M Karplus,et al.  Solution structure of FKBP, a rotamase enzyme and receptor for FK506 and rapamycin , 1991, Science.

[4]  A. Holmes,et al.  SYNTHESIS OF (-)-GLOEOSPORONE , 1991 .

[5]  S. Schreiber,et al.  Inhibition of FKBP rotamase activity by immunosuppressant FK506: twisted amide surrogate. , 1990, Science.

[6]  L. Overman,et al.  Formation of .DELTA.4-oxocenes from Lewis acid promoted cyclizations of 5-hexenyl acetals. Evidence for a concerted ene cyclization mechanism , 1990 .

[7]  L. Overman,et al.  Preparation of eight-membered cyclic ethers by Lewis acid promoted acetal-alkene cyclizations , 1990 .

[8]  A. Holmes,et al.  Synthetic methodology for the preparation of trans- and cis-2,9-disubstituted oxonanes , 1989 .

[9]  S. Schreiber,et al.  Structural and synthetic studies of the spore germination autoinhibitor, gloeosporone. , 1988, Journal of the American Chemical Society.

[10]  L. Overman,et al.  Total synthesis of (-)-laurenyne. Use of acetal-initiated cyclizations to prepare functionalized eight-membered cyclic ethers , 1988 .

[11]  A. Holmes,et al.  A strategy for the asymmetric synthesis of medium ring oxygen heterocycles: Enantioselective total synthesis of (+)-octahydrodeacetyldebromolaurencin , 1988 .

[12]  G. Adam,et al.  Total synthesis of (+)-gloeosporone: assignment of absolute configuration , 1987 .

[13]  W. L. Meyer,et al.  Revised Structure of the Fungal Germination Self-Inhibitor Gloeosporone , 1987 .

[14]  G. S. Cockerill,et al.  A synthesis of pseudo-gloeosporone , 1987 .

[15]  A. Holmes,et al.  Studies on the synthesis of gloeosporone - synthesis of the proposed 2,8-disubstituted oxocane structure , 1986 .

[16]  M. Gelb,et al.  Fluoro ketone inhibitors of hydrolytic enzymes. , 1985, Biochemistry.

[17]  W. L. Meyer,et al.  The structure of gloeosporone, a novel germination self-inhibitor from conidia of Collectotrichum gloeosporioides , 1983 .

[18]  V. Martín,et al.  A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds , 2002 .

[19]  D. Chadwick,et al.  6‐exo‐Hydroxy‐2‐exo‐methylbicyclo[2.2.1]heptane‐2,6‐carbolactone , 1982 .

[20]  D. Seebach,et al.  Crahamimycin A1 synthesis and determination of configuration and chirality , 1982 .

[21]  D. Rowan,et al.  1,7-Dithia and 1-oxa-7-thiaspiro[5.5]undecanes. Excellent systems for the study of stereoelectronic effects (anomeric and exo-anomeric effects) in the monothio and the dithioacetal functions , 1981 .

[22]  L. Horner,et al.  Zur Kenntnis der o-Chinone, 32. Über Konformationsstudien an vicinalen Tetracarbonylverbindungen und über Isomerieerscheinungen bei Formoinen , 1968 .

[23]  J. Sharp,et al.  Trichloromethylation reaction. Ring-chain tautomerism , 1967 .

[24]  J. Sharp,et al.  Trichloromethylation of Anhydrides. Ring—Chain Tautomerism1a , 1965 .

[25]  T. Wieland,et al.  Thioarylwanderung bei Oxocarbonsäure-thioestern , 1963 .

[26]  Yun-Ger Chang,et al.  Ozonolysis of Unsymmetrical Acetylenes , 1962 .

[27]  P. Bailey.  The Reactions Of Ozone With Organic Compounds , 1958 .

[28]  N. Leonard,et al.  The Influence of Steric Configuration on the Ultraviolet Absorption of 1,2-Diketones , 1950 .

[29]  E. Blout,et al.  The Ultraviolet Absorption Spectra of Hindered Benzils , 1950 .