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Studies concerning experimental and mechanistic aspects of the domino allylstannylation/

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Abstract  

Studies concerning experimental and mechanistic aspects of the domino allylstannylation/

Heck reaction of ortho-iodobenzaldehydes and related structures are described. (1) After the

development of general reaction conditions structurally modified substrates were used and a

broad spectrum of 3-methylene-1-indanols could be synthesised. Beside iodides, triflate and

bromides in situ generated imines also proved to be suitable substrates. (2) Mechanistic

investigations using in situ NMR-spectroscopy and X-ray diffractometry showed strong

evidence for an intermediate palladacycle. A new intramolecular, electrophilic activation

mode was postulated which consists of an activation of the aldehyde function through an

adjacent Lewis-acidic Pd

II

-center. Using control experiments it was shown that

alkoxystannanes proved to be possible base equivalents in Heck reactions. (3) An

enantioselective protocol using a model system could be developed by application of chiral

ligands. A systematic ligand screening revealed Taniaphos to be the optimal chiral ligand

with an induced enantiomeric excess of 96%. The established conditions could be applied to

structural modified substrates. (4) The first steps in the synthesis of the natural product

mutisianthol using the domino allylstannylation/Heck reaction as the key step demonstrates

that this transformation generally serves to build up the required indan structural motif.

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