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2142727845
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note
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A reaction mechanism with one catalytic cycle is also possible, where metal carbonyl complex A itself acts as a catalyst for carbonylative coupling. But this mechanism conflicts with highly enantioselective induction by chiral diphosphine (Table 6), since the dissociation of phosphine ligand from the metal center is needed for coordination of an enyne, which is an enantiomerically differentiated step.
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37
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2142667491
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From the sign of optical rotation, the absolute configuration of obtained 2a proved to be S (ref 3b). This means that the mechanism of asymmetric induction with aldehyde as a CO source by the Rh-tolBINAP system is the same as that with CO gas (refs 7 and 8).
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