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Mixed main‐group metal alkyls and alkoxides in synthesis and catalysis
Author(s) -
Screttas Constantinos G.,
Steele Barry R.
Publication year - 2000
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/1099-0739(200010)14:10<653::aid-aoc54>3.0.co;2-s
Subject(s) - chemistry , reagent , magnesium , alkoxide , tetrahydrofuran , allylic rearrangement , organic chemistry , metal , lithium (medication) , potassium , alkali metal , catalysis , solvent , inorganic chemistry , polymer chemistry , medicine , endocrinology
The organic derivatives of sodium and potassium are generally insoluble in hydrocarbons while their instability in ethers, for example, precludes long‐term storage of solutions and thus restricts their wider application. Addition of magnesium 2‐ethoxyethoxide produces hydrocarbon‐soluble reagents with reactivity comparable with that of the simple organometallics. The organoalkali‐metal reagents in the presence of magnesium 2‐ethoxyethoxide in tetrahydrofuran become almost inert towards cleavage of the solvent while retaining organoalkali‐metal‐like metallation characteristics. The metallating ability of organolithium reagents can be modified by addition of suitable metal alkoxides. Mixed alkali‐metal dialkylaminoalkoxides combine the activating properties of an alkoxide with those of a tertiary amine, while magnesium 2‐ethoxyethoxide greatly reduces the metallating ability and unwanted side reactions can be avoided. Certain allylic or benzylic organolithium reagents, in the presence of mixed lithium potassium dialkylaminoalkoxides, and in some cases also of magnesium 2‐ethoxyethoxide, add either stoichiometrically or catalytically to ethylene to produce mono‐ or poly‐ethylated derivatives. In this way substantial quantities of interesting sterically demanding aromatic derivatives have been produced in good yield. Copyright © 2000 John Wiley & Sons, Ltd.