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An unprecedented catalytic asymmetric inverse‐electron‐demand aza‐Diels–Alder reaction of indoles with in situ formed azoalkenes is reported. A diverse set of [2,3]‐fused indoline heterocycles were achieved in generally good yields (up to 97 %) with high regioselectivity and diastereoselectivity (>20:1 d.r.), and with excellent enantioselectivity (up to 99 % ee).
Die gekreuzte 1,3‐dipolare Cycloaddition zwischen zwei unterschiedlichen Yliden (siehe Schema) mit dem chiralen CuI/tBu‐Phosferrox‐Komplex als Katalysator eröffnet einen Zugang zu hoch funktionalisierten 1,2,4‐Triazinan‐Derivaten. Unter milden Bedingungen werden die Produkte in guten Ausbeuten mit ausgezeichneten Diastereo‐ und Enantioselektivitäten erhalten.
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