Abstract
Enantioselective intramolecular arylcyanation of olefins is achieved
by a Ni(cod)2/chiral phosphinoxazoline/AlMe2Cl
catalyst to give chiral, substituted indoline derivatives bearing
a benzylic quaternary stereocenter in high yields with good to excellent enantioselectivities.
Key words
asymmetric synthesis - carbocyanation - C-C
bond activation - nickel - indoline
References and Notes
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General Experimental
Procedure:
An aryl cyanide (0.50 mmol)
and a solution of AlMe2Cl (1.04 M in hexane, 0.20 mL,
0.20 mmol) were added sequentially to a solution of Ni(cod)2 (13.8
mg, 50 µmol) and a ligand (50 µmol) in 1,2-dimethoxyethane
(0.50 mL) prepared in a 3 mL vial under an argon atmosphere in a
dry-box. The vial was sealed with a screw-cap, taken outside the
dry-box and heated at 100 ˚C for the time specified
Table
[¹]
. The resulting
mixture was filtered through a silica gel pad, concentrated in vacuo,
and purified by flash column chromatography on silica gel to give
the corresponding arylcyanation products in the yields listed in
Table
[¹]
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See Supporting Information for details
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The presented conditions were completely
ineffective for
N-methyl-N-(2-cyanophenyl)methacrylamide
