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General Procedure for CM Reactions at Room Temperature: A solu-
tion of allylbenzene (59 mg, 0.5 mmol, 1.0 equiv.), cis-1,4-diace-
toxy-2-butene (206 mg, 1.2 mmol, 2.4 equiv.) and Ru catalyst
(1 mol-%) in CH2Cl2 (5 mL) was stirred under an Ar atmosphere
at room temp. Reaction conversion was monitored by 1H NMR
analysis on 0.5 mL aliquots quenched with ethyl vinyl ether (1 mL).
Peaks corresponding to the E isomer at δ = 4.57 ppm and the Z
isomer at δ = 4.77 ppm were compared using a 500 MHz NMR
spectrometer.
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General Procedure for RCM Reactions of Diethyl Diallylmalonate
(DEDAM) and 2-Allyl-2-(2-methylallyl)malonate at Room Tempera-
ture: A 12 μL aliquot of substrate was introduced into a dry NMR
tube under argon using a dry micro-syringe. To this was introduced
0.5–0.6 mL of dry, CD2Cl2 (containing 0.1 mol-% catalyst) from
1.5 m stock solutions of catalysts. The tubes were sealed with an
air-tight septum and quickly introduced into NMR probes and ac-
quisitions were made at regular intervals. Conversions were calcu-
lated from 1H NMR by comparing peak integrations at δ =
4.93 ppm (diethyl cyclopent-3-ene-1,1-dicarboxylate, ethylenic H
peaks) and at δ = 4.55 ppm (diethyl diallylmalonate, allyl H peaks)
and at δ = 5. 18 ppm (diethyl 3-methylcyclopent-3-ene-1,1-dicarb-
1
oxylate, ethylenic H peak) and δ = 5.64–5.75 [diethyl 2-allyl-2-(2-
methylallyl)malonate, unsubstituted allyl 1H peak] using
500 MHz spectrometer.
a
Supporting Information (see footnote on the first page of this arti-
cle): Full experimental details and characterizations are provided
in the Supporting Information.
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Acknowledgments
The authors thank the Agence Nationale de la Recherche (ANR)
(ANR-09-CP2D-11-01, NanoremCat2) for financial support and a
PhD funding to S. S.
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