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The Application of Trimethylsilyl Diazomethane to the Synthesis of Optically Active Pyrazolines and Related Studies


Mish, Michael Robert (2001) The Application of Trimethylsilyl Diazomethane to the Synthesis of Optically Active Pyrazolines and Related Studies. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/s6ej-q525.


The 1,3-dipolar cycloadditions of trimethylsilyl diazomethane with camphorsultam-derived acrylates are reported as a means for the efficient synthesis of optically active pyrazolines. Trimethylsilyl diazomethane is a safe, commercially available diazoalkane which provides Δ1-pyrazolines 1n good yield and diastereoselectivity when camphorsultam-derived acrylates are used as the reaction dipolarophiles . These initial cycloadducts are subsequently converted to stable, characterizable Δ2-pyrazolines upon desilylation.

A manifold of reactions that can be applied to these Δ2-pyrazolines has been developed which includes pyrazoline reduction, N-N bond reduction, addition to the pyrazoline C=N by mild carbon nucleophiles, and both solvolytic and reductive chiral auxiliary removal. Additionally, it has been demonstrated that the pyrazoline reduction products can take part in peptide coupling reactions that allow for the pyrazolidines to serve as proline-like molecules. The development of this methodology is a general solution to the problem of highly substituted, functionalized pyrazoline synthesis. Importantly, the pyrazolines thus provided have been demonstrated to be amenable to reactions that add to their value as synthetic intermediates.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry,trimethylsilyl diazomethane, pyrazolines, synthesis
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Carreira, Erick Moran
Thesis Committee:
  • Dougherty, Dennis A. (chair)
  • Carreira, Erick Moran
  • Dervan, Peter B.
  • Grubbs, Robert H.
Defense Date:7 September 2000
Record Number:CaltechTHESIS:03252014-083524220
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8164
Deposited By: Dan Anguka
Deposited On:25 Mar 2014 16:39
Last Modified:29 Nov 2022 22:54

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