The document describes new catalytic reactions developed by David Milstein for green synthesis and sustainable energy. These reactions are catalyzed by pincer-type ruthenium complexes and involve aromatization-dearomatization of the ligand. The reactions allow for (a) coupling of alcohols to form esters and H2, (b) hydrogenation of esters to alcohols under mild conditions, (c) coupling of amines with alcohols to form amides with H2 liberation, (d) synthesis of primary amines from alcohols and ammonia, and (e) direct formation of acetals by coupling of alcohols, and proceed under neutral conditions without waste
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2010 Abstract Milstein
The document describes new catalytic reactions developed by David Milstein for green synthesis and sustainable energy. These reactions are catalyzed by pincer-type ruthenium complexes and involve aromatization-dearomatization of the ligand. The reactions allow for (a) coupling of alcohols to form esters and H2, (b) hydrogenation of esters to alcohols under mild conditions, (c) coupling of amines with alcohols to form amides with H2 liberation, (d) synthesis of primary amines from alcohols and ammonia, and (e) direct formation of acetals by coupling of alcohols, and proceed under neutral conditions without waste
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Design of New Catalytic Reactions for Green Synthesis and
Sustainable Energy David Milstein Department of Organic Chemistry, The Weizmann Institute of Science Rehovot 76100, Israel E-mail: [email protected]
We have developed a new mode of metal-ligand cooperation, based on
aromatization-dearomatization
of
pincer-type
ligands,
and
have
designed
environmentally benign catalytic reactions based on such cooperation, including (a)
dehydrogenative coupling of alcohols to form esters and H2 (b) hydrogenation of esters to alcohols under mild conditions (c) coupling of amines with alcohols to form amides with liberation of H2 (d) selective synthesis of primary amines directly from alcohols and ammonia (e) direct formation of acetals by dehydrogenative coupling of alcohols. These reactions are efficient, proceed under neutral conditions and produce no waste. They are catalyzed by pincer-type ruthenium complexes based on pyridine and on acridine, and involve as a key mechanistic step aromatizationdearomatization of the hetero-aromatic ligand core. Metal-ligand cooperation of this type has very recently led also to a distinct approach towards water splitting, based on consecutive thermal H2 generation and light-induced O2 liberation.