Synthesis and Diels-Alder Reactivity of 5,6,7,8-Tetramethylidene-2-bicyclo[2.2.2]octanol and -octanone. Selective Oxidations of the Corresponding Bis(irontricarbonyl) Complexes |
| |
Authors: | Raphy Gabioud Pierre Vogel |
| |
Abstract: | Hydroboration of the syn, anti-Fe(CO)3]2 double complex 24 of the readily available 5,6,7,8-tetramethylidene-2-bicyclo2.2.2]octene ( 22 ) gave the corresponding doubly complexed 2-bicyclo2.2.2]octanol 25. CrO3-oxidation furnished ketone 27 . The syn-Fe(CO)3-groups in 25 and 27 were oxidized selectively with trimethyl-amine oxide and yielded the corresponding anti-Fe(CO3)-monocomplexed tetraenes 26 and 28. The anti-Fe(CO)3-group in 28 could be removed, and 5,6,7,8-tetramethylidene-2-bicyclo2.2.2]octanone ( 11 ) was obtained. NaBH4-reduction of 11 afforded tetraenol 10. TCE-cycloadditions to 10 and 11 (k1) were at least 10 times as fast as those (k2) to the corresponding monoadducts 35/36 and 34 , respectively. This Diels-Alder reactivity difference vanishes (k1 ≈ k2) with methyl propynoate. The latter dienophile added to the anti-Fe(CO)3-monocomplexed tetraenone 28 with ‘para’-regioselectivity. |
| |
Keywords: | |
|
|