Enantioselective Stereodivergent Nucleophile‐Dependent Isothiourea‐Catalysed Domino Reactions

α,β‐Unsaturated acyl ammoniums generated from the reaction of α,β‐unsaturated 2,4,6‐trichlorophenol (TCP) esters bearing a pendent enone with an isothiourea organocatalyst are versatile intermediates in a range of enantioselective nucleophile‐dependent domino processes to form complex products of diverse topology with excellent stereoselectivity. Use of either 1,3‐dicarbonyls, acyl benzothiazoles, or acyl benzimidazoles as nucleophiles allows three distinct, diastereodivergent domino reaction pathways to be accessed to form various fused polycyclic cores containing multiple contiguous stereocentres.