Arylalkoxylation of Alkynes & Olefins via Transition Metal-Catalyzed C–O Activation Mary P. Watson, Department of Chemistry & Biochemistry, University of Delaware In our pursuit to exploit transition metal-catalyzed activation of C–O bonds for the rapid generation of molecular and stereochemistry complexity, we have developed new reactions of both strong C–O bonds and weaker C–N bonds. We are excited to pursue the discovery of new reaction technology in these areas. We have developed a Heck cross coupling of aryl pivalates. This is one of the first examples of C–C bond formation via activation of a strong C–O bond with a nonorganometallic coupling partner.
R1
10 mol % Ni(cod)2 12 mol % dppf
OPiv +
R2 K3PO4 (1.5 equiv) PhMe (0.4 M) 125–150 °C
R1
P P Ni OPiv
R1
PPh2
R2 Fe
20 examples up to 94%
PPh2 dppf
We have developed stereospecific coupling of benzylic ammonium salts with boronic acids. This is the first example of a stereospecific coupling of a benzylic electrophile with a boronic acid.
