10.1002/adsc.201701568
Advanced Synthesis & Catalysis
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Ph2Se2 reacts cleanly with KN(SiMe3)2 to provide easy
access to the selenolate anion PhSe−, without the
necessity of isolation nor purification, and which also
catalyzes the conversion of benzyl halides into trans-
stilbenes. Reactivity studies in combination with
control experiments and independent syntheses
provided strong evidence for the intermediacy of
species such as PhSeK (A), PhSeCH2Ph (B), and
PhSeCHPhCH2Ph (E). Based on these studies, we
conjecture that selenolate anions have significant
potential in organocatalysis by taking advantage of
their ability to stabilize carbanions and also promote
C=C formation via an E2 mechanism. Other related
reactions that are catalyzed by this novel class of
catalysts are currently under investigation in our
laboratories.
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Experimental Section
General Procedure for Catalysis with Diphenyl
Diselenide: To an oven-dried microwave vial equipped with
a stir bar was added diphenyl diselenide and KN(SiMe3)2
(3.0 equiv for entries 1-7 and 13 (Table 3), or 1.5 equiv for
entries 8-12 (Table 3)), under nitrogen atmosphere followed
by 1.5 mL (entries 1-7 and 13, Table 3) or 0.5 mL (entries
o
8-12, Table 3) dry DME at 21 C. The microwave vial was
sealed with a cap containing a septum. Benzyl chloride (23
μL, 0.20 mmol) in dry DME was added by syringe pump (5
µL/ min, 0.1 M) to a solution of the diphenyl diselenide with
KN(SiMe3)2 for entries 1-7 and 13, (30 µL/ min, 0.2 M, for
entries 8-12. After the reaction was complete (defined by
screening of the reaction mixture by 1H NMR spectroscopy
and TLC), the sealed vial was opened to air, and the reaction
mixture was passed through a short pad of silica gel. The
pad was then rinsed with 10 mL of ethyl acetate and the
solvent was removed under reduced pressure. The crude
product was purified by dissolving in hexanes, filtering
through a short pad of silica gel, and solvent removed under
reduced pressure. The residue was washed with 3-5 mL cold
pentane or flash chromatography on silica gel (eluted with
hexanes). For further details of the synthesis and
characterization, see the Supporting Information.
Acknowledgements
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821-841.
We thank the National Science Foundation (CHE-1464744) for
financial support. DJM thanks the University of Pennsylvania for
startup funds. O.S.T. acknowledges financial support from
FONDECYT/ Postdoctorado no 3160270.
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