DNA Base-Flipping and Hammett Studies of Asymmetric Palladium Catalysis

6/14/01


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Table of Contents

DNA Base-Flipping and Hammett Studies of Asymmetric Palladium Catalysis

PPT Slide

Base-Flipping

Uracil DNA Glycosylase (UDG)

UDG-DNA Crystal Structure

Which Happens First?

UDG: Flips out via Major Groove

Oversimplified Rationale

Initial Route - DNA Base Last

N-Glycoside Formation

dU Starting Material Route

Dinucleotide Formation

Mononucleotide Formation

DNA Dodecamer

DNA Numbering Scheme

1H NMR (D2O) 400 MHz

Base (H6/H8) to H1’ NOEs

400 MHz NOESY

H6/H8 & H1’ Assignments

Imino Hydrogens

Imino Assignments

Future Work and Directions

Middlebury’s Seasons

Pd-Catalyzed Allylic-Alkylation

Selective Nucleophilic Addition

Phosphinooxazoline Ligands

Modified Ligands

Literature Precedent

Ligand Synthesis

Preliminary Alkylation Results

p-Allyl Complex Formation

COSY of Allyl Hydrogens

13C NMR Shifts by HSQC

13C NMR Correlations with ee

Conclusions and Future Work

Acknowledgements

 Author: Rick Bunt

Email: rbunt@middlebury.edu

Home Page: http://www.middlebury.edu/~rbunt/