Intramolecular cyclization of organometallic compounds represents
a promising tool for synthesis in general. The use of strategically-
placed heteroatoms in the cyclizing molecule can influence
the stereochemistry and/or efficiency of an organometallic cyclization
while providing for functionality in the cyclic product.
The work described herein first concerns cyclizations of organolithiums....
The tosylhydrazones of 2-heptanone, 4,4-dimethy1-2-
heptanone, 6-heptyn-2-one and 4,4-dimethy1-6-heptyn-2-
one were synthesized and decomposed under a variety of
reaction conditions: dry lithium and sodium salt pyrolyses,
sodium methoxide thermolyses in diglyme and photolyses of
the lithium salt in tetrahydrofuran. The saturated analogues
2-heptanone tosylhydrazone and its 4,4-dimethyl
isomer afforded the...
The photochemistry of some analogs of insect growth regulators
(IGR's) was studied. Methyl geranate, TY, was synthesized and the
mechanisms of its photochemical reaction pathways were studied by a
variety of techniques. Direct irradiation of 71 in ether leads to the
formation of five new products: 98, the product of...