Alexandria Digital Research Library

Silylcupration of Conjugated Alkynes and Copper-Hydride Reductions of Morita-Baylis-Hillman Adducts

Author:
Peterson, Carl August
Degree Grantor:
University of California, Santa Barbara. Chemistry
Degree Supervisor:
Bruce H. Lipshutz
Place of Publication:
[Santa Barbara, Calif.]
Publisher:
University of California, Santa Barbara
Creation Date:
2015
Issued Date:
2015
Topics:
Organic chemistry
Genres:
Online resources and Dissertations, Academic
Dissertation:
M.S.--University of California, Santa Barbara, 2015
Description:

There currently exists a need for more extensive mild and greener bond forming reactions that allow for construction of sophisticated carbon frameworks. Vinylsilanes have proven themselves to be valuable intermediates in organic synthesis. Traditionally, these educts have been difficult to access requiring stoichiometric metals which often precudes their use on scale. Herein, we investigated the use of Suginome's reagent, PhMe2SiBpin, in a commercially available surfactant TPGS-750-M to afford isomerically pure (E)-beta-silyl-substituted carbonyl derivatives by way of a copper catalyzed silylcupration in water at room temperature.

Copper hydride has seen extensive use as both an asymmetric and achiral source of hydride for many decades. We were interested in investigating copper hydride's application toward Morita-Baylis-Hillman adducts given their possession of multiple electrophilic sites. We discovered that CuH could be used for tandem reductions of racemic MBH ketones lacking defined olefin geometry into valuable chiral allylic alcohol derivatives with defined stereochemistry.

Physical Description:
1 online resource (101 pages)
Format:
Text
Collection(s):
UCSB electronic theses and dissertations
ARK:
ark:/48907/f3w958qk
ISBN:
9781339471600
Catalog System Number:
990046180050203776
Rights:
Inc.icon only.dark In Copyright
Copyright Holder:
Carl Peterson
File Description
Access: Public access
Peterson_ucsb_0035N_12751.pdf pdf (Portable Document Format)