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Glycosylidene Carbenes. Part 13. Synthesis and thermolysis of representative 1‐azi‐glycoses
Author(s) -
Vasella Andrea,
Witzig Christian,
Waldraff Christian,
Uhlmann Peter,
Briner Karin,
Bernet Bruno,
Panza Luigi,
Husi René
Publication year - 1993
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19930760811
Subject(s) - chemistry , diazirine , thermal decomposition , benzaldehyde , heterolysis , oxime , enol , medicinal chemistry , stannane , acetophenone , organic chemistry , photochemistry , catalysis
In the context of the hypothesis postlating a heterolytic cleavage of a CN bond during thermolysis of alkoxydiazirines ( Scheme 1 ), we report the preparation of the diazirines 4 , 5 , 7 , and 8 , the kinetic parameters for the thermolysis in MeOH of the diazirines 1 and 4–9 , and the products of their thermolysis in an aprotic environment. The diazirines 4 , 57 , and 8 ( Scheme 2–5 ) were prepared from the known hemiacetals 10 , 19 , 34 (prepared from 31 in an improved way), and 42 according to an established method. The oximes 11 , 20 , 35 , and 43 were obtained from the corresponding hemiacetals as ( E/Z )‐mixtures; 43 was formed together with the cyclic hydroxylamine 44 . Oxidation of 11 , 35 , and 43 ( N ‐chlorosuccinimide/1,8‐diazabicyclo[5.4.0]undec‐7‐ene (NCS/DBU) or NaIO 4 ) gave good yields of the ( Z )‐hydroximolactones 12 , 36 , and 45 , while the oxime 20 led to a mixture of the ( E )‐ and ( Z )‐hydroximolactones 21 and 22 , which adopt different conformations. Their configuration was assigned, inter alia , by a comparison with the enol ethers 28 and 29 , which were obtained, together with 30 , from the reaction of the diazirine 5 with benzaldehyde and PBu 3 . Treatment of the hydroximolactone O ‐sulfonates 13 , 23 , 37 , and 46 with NH 3 /MeOH afforded the diaziridines 15 , 25 , 38 , and 47 in good yields, while the ( E )‐sulfonate 24 decomposed readily. Oxidation of the diaziridines gave 4 , 5 , 7 , and 8 , respectively. Thermolysis of the diazirines 1 and 4–9 in MeOH yielded the anomeric methyl glycosides 50/51 , 16/17 , 26/27 , 52/53 , 39/40 , 48/49 , and 54/55 , respectively. A comparison of the kinetic data of the thermolysis at four different temperatures shows the importance of conformational and electronic factors and is compatible with the hypothesis of a heterolytic cleavage of a CN bond. An early transition state is evidenced by the absence of torsional strain by an annulated 1,3‐dioxane ring. Thermolysis of 1 in MeCN at 23° led mostly to the diasteroisomeric ( Z,Z )‐, ( E,E )‐, and ( E,Z )‐lactone azines 56 , 57 , and 58 ( Scheme 6 ), which convert to 56 under mild conditions, and to 59 (3%). The benzyloxyglucal 59 was obtained in higher yields (18%), together with 44% of 56–58 , by thermolysis of solid 1 . Similarly, thermolysis at higher temperatures of 4 in toluene, THF, or dioxane and of 9 in CH 2 Cl 2 or THF yielded the ( Z,Z )‐lactone azines 60 and 61 , respectively, the latter being accompanied by the dihydro‐oxazole 62 .