Preparation and use of (2-butene-1,4-diyl) magnesium complexes i

Details Preparation and use of (2-butene-1,4-diyl) magnesium complexes i Preparation and use of (2-butene-1,4-diyl) magnesium complexes i

1994-10-17

1996-12-03

Shaver, Paul F.

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

556460, 556449, 556465, 260665R, 585360, 585361, 585407, 568374, 568819, C07F 722, C07F 724, C07F 730

Patent

active

055810047

ABSTRACT:
The magnesium complexes of cyclic hydrocarbons and conjugated dienes, such as 1,2-dimethylenecycloalkanes and 1,3-butadienes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4-diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, alkylditriflates, bromoalkylnitriles, esters, or amides serve as a convenient method for synthesizing carbocyclic systems. Significantly, carbocycles prepared by this method contain functional groups such as the exocyclic double bond or a keto group in one of the rings which could be used for further elaboration of these molecules. Furthermore, fused bicyclic systems containing a substituted five-membered ring can be conveniently prepared at high temperatures by the reactions of (2-butene-1,4-diyl)magnesium complexes with carboxylic esters or acid halides whereas low temperatures lead to regioselective synthesis of .beta.,.gamma.-unsaturated ketones. Additionally, .gamma.-lactones, including spiro .gamma.-lactones, can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with a ketone or aldehyde and carbon dioxide.

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