Schaefer, Phillip Cuthbert (1969) Squalene cyclization. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-10032002-124237
It has been observed that the proton, which is located at C-14 in squalene or C-13 in the "presterol cation," migrates less than 10% of the time (with a confidence level of 74%) to C-20 in lanosterol, and therefore 90% of the time (with a confidence level of 74%) to C-17 in lanosterol. If enzymatically controlled reactions are stereospecific, then at C-13/C17/C-20 in the "presterol cation," there are two sequential 1, 2-migrations during the backbone rearrangement to form lanosterol. A theoretical interpretation of this observation, which reflects on the stereochemistry of the C-18/C-19 double bond of squalene just prior to cyclization, is presented.
A theoretical discussion of the minimal requirements for binding squalene-2, 3-oxide to an enzyme in order to obtain complete stereochemical control over the product is presented.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||9 September 1968|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||04 Oct 2002|
|Last Modified:||26 Dec 2012 03:03|
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