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Boyer's Reaction and Transetherification : Mechanism and New Perspectives
Author(s) -
Fraschetti Caterina,
Speranza Maurizio,
Guarcini Laura,
Roselli Graziella,
Filippi Antonello
Publication year - 2016
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22581
Subject(s) - chemistry , adduct , catalysis , reactivity (psychology) , alcohol , reaction mechanism , cyclohexane , chirality (physics) , computational chemistry , organic chemistry , medicinal chemistry , combinatorial chemistry , stereochemistry , medicine , chiral symmetry breaking , alternative medicine , physics , pathology , quantum mechanics , nambu–jona lasinio model , quark
The progress and stereochemistry of Boyer's reaction were analyzed using several simple, chiral, alcoholic substrates, a variable amount of BiBr 3 and different solvents. Basic solvents inhibit the reaction, while cyclohexane works very well; thus, it was our choice for the present study. In contrast to previous works, BiBr 3 behaves as a true catalyst, being not consumed during the reaction. Although poisoning of the catalyst occurs to some extent, it does not prejudice the reaction yields (>90%). Gas chromatography/mass spectrometry (GC–MS) monitoring of the reaction revealed that, for example, in the presence of alcohol rac-1 , isomeric ethers 4 transetherificate to 3 . We propose a unifying mechanistic model for both Boyer's and transetherification reactions, in which the electronic properties of n‐adducts intermediates, formed by combination of bismuth(III) of BiBr 3 and oxygen atoms of alcohols and ethers, play the key role for both the reactivity and the stereochemical outcome of the reaction. Chirality 28:269–275, 2016 . © 2016 Wiley Periodicals, Inc.