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In general, Pd-catalyzed allylic substitutions with 'soft' nucleophiles involve nucleophilic attack directly on the allyl unit, on the opposite face to that occupied by the metal. This is contrasted with the situation for 'hard' nucleophiles where the initial attack occurs at the metal, with subsequent migration of the nucleophile to the allyl moiety-the addition to the allyl unit therefore occurring from the same face as the metal. Obviously, this has profound implications on the stereochemical outcome
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In general, Pd-catalyzed allylic substitutions with 'soft' nucleophiles involve nucleophilic attack directly on the allyl unit, on the opposite face to that occupied by the metal. This is contrasted with the situation for 'hard' nucleophiles where the initial attack occurs at the metal, with subsequent migration of the nucleophile to the allyl moiety-the addition to the allyl unit therefore occurring from the same face as the metal. Obviously, this has profound implications on the stereochemical outcome.
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[16] these higher-energy species generally do not play a rô le in the catalytic cycle, so they can be ignored in the mechanistic discussion
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[16] these higher-energy species generally do not play a rô le in the catalytic cycle, so they can be ignored in the mechanistic discussion.
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18
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84949974588
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3- complex
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3- complex.
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20
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84949934758
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[16] Nevertheless, in most cases, the interchange is rapid compared with the rate of nucleophilic attack and, therefore, the product outcome does not necessarily depend on the intermediate isomer ratio (Curtin-Hammett principle)
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