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Since different cycloadducts may provide different response from the detector of the GC, an equimolar amount of two different cycloadducts may not provide exactly a 1:1 ratio of peak areas on the GC integration. Thus, equimolar amount of each cycloadduct was injected into the GC and their integration areas were compared. These numbers were then used to correct for the product ratios.
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As noted by a reviewer, the observed relative rate of cycloaddition may not be purely from an electronic effect. The coordinating ability of the 7-substutuent that competes with the anti-π-bond for the metal center could also be a factor in the observed rate difference.
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Optimized geometries for all the structures mentioned in the text are reported in the Supporting Information.
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49
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The regiochemistry of metallacyclopentenes 15(B) and 15a,d,f is opposite that proposed by Cheng and co-workers in the nickel-catalyzed coupling and cyclization reactions between oxanorbornenes and alkyl propiolates. The difference in regiochemistry could be due to the use of different metal catalyst (nickel vs ruthenium), and the oxygen in the oxanorbornenes used in Cheng's study could coordinate to the metal but not in our case with norbornadienes. Also, there are no theoretical calculations to support the proposed mechanism/ structure by Cheng: (a) Rayabarapu, D. K.; Cheng, C.-H. Angew. Chem., Int. Ed. 2001, 40, 1286.
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