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Preparative Polar Organometallic Chemistry is a collection of
laboratory procedures for the synthesis and functionalization of
organoalkali and Grignard compounds. The second volume with methods
for generation and transformation of compounds bearing the metal at
an sp3 carbon complements the first in which the metal was bound to
an sp2 carbon atom in the reagent. Synthetically important
intermediates such as metallated S, S-acetales, imines, nitriles,
isonitriles and ketones are illustrated. All procedures have been
worked out in full detail and tested in the author's own
laboratory. Both books are intended to be practical bench-top
laboratory manuals for working organic chemists, from the student
to the advanced scientist.
Polar organometallic compounds are indispensable for the synthetic
chemist. As this book shows, these almost ideal reagents are easy
to prepare with high specificity under mild conditions and yet
react quite readily with a great variety of substrates. Many
compounds can be metallated directly at positions which would
otherwise be difficult to substitute. Functional groups and
heteroatoms already present in a molecule direct metallation to
sites in their vicinity. The rules which govern polar
organometallic chemistry often are not dominated by the usual
n-delocalization and inductive effects; dipolar interactions,
chelation, polarization, etc. often can be much more important.
This affords novel synthetic opportunities. A good example is the
development of a basically new type of aromatic substitution
chemistry not based on positively charged intermediates. Seebach's
injunction, "Thinking of polar organometallic compounds as
carbanions is an impoverishment rather than a simplification"
(International Symposium, Chemistry of Carbanions, Durham 1984),
stresses the need to consider the metal not only as an integral,
but perhaps also as the key component of these reagents. Rather
than wandering off as solvated cations and acting as uninvolved
spectators, the metals, rather than the anion moieties, can
initiate and govern the subsequent reactions. To the founders of
this field, e. g. Grignard, Ziegler, Gilman, Wittig, and their
followers, the metal was critical. The title of Schlosser's book,
"Polare Organometalle," certainly was apt.
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