University of Illinois

Rulin Ma

M Christina White

Stephen E Ammann

Wei Liu

The enantioselective synthesis of isochroman motifs has been accomplished via Pd(II)-catalyzed allylic C&#x2014;H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C&#x2014;H oxidation reaction proceeds with the broadest scope and highest levels asymmetric induction reported to date (avg. 92% ee, 13 examples &#x2265;90% ee). Additionally, C(sp)-N fragment coupling reaction between abundant terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/sulfoxide (SOX) catalyzed intermolecular allylic C&#x2014;H amination is disclosed. A range of 52 allylic amines are furnished in good yields (avg. 76%) and excellent regio- and stereoselectivity (avg. &#x3e;20:1 linear:branched, &#x3e;20:1 E:Z). For the first time, a variety of singly activated aromatic and aliphatic nitrogen nucleophiles, including ones with stereochemical elements, can be used in fragment coupling stiochiometries for intermolecular C&#x2014;H amination reactions.

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Urbana, IL, United States of America

Rulin Ma