ChemInform Abstract: RING CLOSURE REACTIONS. PART 23. KINETICS OF FORMATION OF THREE- TO SEVEN-MEMBERED-RING N-TOSYLAZACYCLOALKANES. THE ROLE OF RING STRAIN IN SMALL- AND COMMON-SIZED-RING FORMATION

1985 ◽  
Vol 16 (52) ◽  
Author(s):  
A. DI MARTINO ◽  
C. GALLI ◽  
P. GARGANO ◽  
L. MANDOLINI
Keyword(s):  
Membered Ring ◽  
Ring Formation ◽  
Ring Closure ◽  
Ring Strain ◽  
Kinetics Of Formation ◽  
Kinetics Of

On the Concerted Ring Opening of Protonated Squalene Oxide and A-Ring Formation in the Biosynthesis of Lanosterol

2003 ◽  
Vol 68 (1) ◽  
pp. 202-210 ◽  
Author(s):  
B. Andes Hess
Keyword(s):  
Ring Opening ◽  
Density Functional ◽  
Reaction Pathway ◽  
Ring Expansion ◽  
Membered Ring ◽  
Ring Formation ◽  
Ring Closure ◽  
Primary Role ◽  
Transition Structure

Density functional calculations were performed on a model system of squalene oxide to study the mechanism of the formation of ring A in the biosynthesis of lanosterol from squalene. When (2Z)-6,7-epoxy-3,7-dimethyloct-2-ene was protonated, it was calculated to undergo a very facile ring opening of the oxirane in concert with the formation of the six-membered ring of the 4-(hydroxymethyl)-1,2,3,3-tetramethy1cyclohexyl cation. A study of the reaction pathway (IRC) indicates a very early transition structure in which the carbon- carbon double bond participates anchimerically in the ring-opening of the protonated oxirane. It is suggested that the primary role of the enzyme in this first step of the biosynthesis of lanosterol is protonation of the oxirane ring along with holding the substrate in the proper conformation for the concerted ring-closure to occur. The similarity between this mechanism and that recently proposed for concerted C-ring expansion and D-ring formation in the biosynthesis of lanosterol is discussed.

Role of ionic strength in the kinetics of formation of the monochelate of nickel(II) with heptane-3,5-dione

1992 ◽  
Vol 24 (4) ◽  
pp. 359-368 ◽  
Author(s):  
María Luisa Moyá ◽  
Amalia Rodriguez ◽  
Francisco Sánchez ◽  
Carlos Blanco ◽  
Michael J. Hynes
Keyword(s):  
Ionic Strength ◽  
Kinetics Of Formation ◽  
Kinetics Of
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