ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Under basic conditions, H2O reacts with tricarbonyl[(1R,2R,3S,4S,5R,6S)-C,5,6,C-η-(2-exo,3-exo-bis-(chloromethyl)-5,6-dimethylidene-7-oxabicyclo[2.2.1]heptane)]iron) (1), and -ruthenium (4), with tricarbonyl-[(1R,2R,3S,4S)-C,2,3,C-η-(2,3,5,6-teramethylidene)-7-oxabicyclo[2.2.1]heptane)]iron (6) and -ruthenium (7), and with cis-η-[1S,2S,3R,4S,5S,6R)-C,2,3,C-η : C-η-(2,3,5,6-tetramethylidene-7-oxabicyclo)[2.2.1]heptane)bis-(tricarbonyliron) (11)] to give products of demetallation and 1,2- or/and 1,4-hydrogenation. Reductive demetallation of tricarbonyl[C,5,6,C-η-(1-(dimethoxymethyl)-5,6-dimethylidenecylohexa-1,3-diene]iron (14) required heating under acidic conditions, giving 2,3-dimethylbenzaldehyde (16). H2O reacted under neutral conditions with cis-heptacarbonyl-μ-[(1RS,2SR,3RS,4SR,5RS,6SR)-2,3-η : C,5,6,C-η-(1-(dimethyoxymethyl)-5,6,-(dimethylidene-7-oxabicyclo[2.2.1]hept-2-ene]diiron (17) and with tricaboyl[(1RS,2SR,3RS,4SR,5RS,6SR)-C-η5,6,C-η-(1-(dimethyoxymethyl)-5,6-dimethyldidene-7-oxabicyclo[2.2.1]hept-2-ene)]iron (18) to give the orthoquinodimethane complex 14 as major product. This reaction was accompanied by hydrogenolysis of the allylic ethereal C(4)—O(7) bond in 17 and 18 and gave tricarbonyl[(1RS,5RS,6SR)-C,5,6,C-η-(1-(dimethoxymethyl)-5,6-dimethylidenecylohex-2-en-1-ol)]iron (21) as minor product. The latter was not an intermediated of reaction 17 → 14. Reactions with D2O allowed one to discuss the possible mechanism of this deoxygenation process. With Trans-heptacarbonyl-μ-[(1RS,2SR,3RS,4SR,5RS,6SR)-2,3-η : C,5,6,C-η-(1-(dimethoxymethyl-5,6-dimethylidene-7-oxabicyclo[2.2.1]-hept-2-ene)diiron (38)], the reaction with THF/H2O gave 14 nearly quantitatively, with no D-incorporation in the presence of D2O.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19880710547
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