Application of Marcus-like equations to group-transfer reactions. A theoretical test of intrinsic barrier additivity and the "square" relationship

1984 ◽  
Vol 106 (17) ◽  
pp. 4724-4735 ◽  
Author(s):  
Jane Donnella ◽  
Joseph R. Murdoch
Keyword(s):  
Transfer Reactions ◽  
Group Transfer ◽  
Theoretical Test

Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4′-bipyridine cocrystal with their crystal structures

2014 ◽  
Vol 70 (11) ◽  
pp. 1040-1045 ◽  
Author(s):  
Majid I. Tamboli ◽  
Vir Bahadur ◽  
Rajesh G. Gonnade ◽  
Mysore S. Shashidhar
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Transfer Reaction ◽  
Acyl Transfer ◽  
Transfer Reactions ◽  
Group Transfer ◽  
Hydrogen Bonding Interactions ◽  
Benzoyl Group ◽  
The Stability ◽  
Group Migration

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8,(1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4′-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2,(1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In(1), molecules are assembled around the crystallographic twofold screw axis (baxis) to form a helical self-assembly through conventional O—H...O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal(1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O—H...N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.

ChemInform Abstract: GROUP TRANSFER REACTIONS VIA PENTAVALENT PHOSPHORUS INTERMEDIATES

1977 ◽  
Vol 8 (23) ◽  
pp. no-no
Author(s):  
W. G. VONCKEN ◽  
A. M. C. F. CASTELIJNS ◽  
S. A. J. DE LEEUW ◽  
H. M. BUCK
Keyword(s):  
Transfer Reactions ◽  
Pentavalent Phosphorus ◽  
Group Transfer ◽  
Abstract Group
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