Hydroamidation of 1,3-dienes with carboxamides remains underdeveloped, particularly for anti-Markovnikov selectivity. We report a disilane-mediated silicon relay strategy in which palladium-catalyzed 1,4-silylamidation generates an allylsilane intermediate that undergoes protodesilylation to furnish the first formal anti-Markovnikov hydroamidation of 1,3-dienes. Suppression of protodesilylation selectively affords 1,4-silylamidation products. Experimental and computational studies clarify the origin of the divergent reaction outcomes.
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Katayama et al. (2026) studied this question.
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