One‐Pot Three‐Component Synthesis of Vicinal Diamines via In Situ Aminal Formation and Carboamination. Issue 41 (16th September 2016)

• Record Type: Journal Article
• Authors: Orcel, Ugo; Waser, Jerome
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 41(2016)
• Page Start: 12881
• Page End: 12885
• Publication Date: 2016-09-16
• Subjects: alkenes -- aminals -- homogeneous catalysis -- Pd catalysis -- vicinal diamines; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201607318
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A synthesis of vicinal diamines via in situ aminal formation and carboamination of allyl amines is reported. Employing highly electron‐poor trifluoromethyl aldimines in their stable hemiaminal form was key to enable both a fast and complete aminal formation as well as the palladium‐catalyzed carboamination step. The conditions developed allow the introduction of a wide variety of alkynyl, vinyl, aryl, and hetereoaryl groups with complete regioselectivity and high diastereoselectivity. The reaction exhibits a high functional‐group tolerance. Importantly, either nitrogen atom of the imidazolidine products can be selectively deprotected, while removal of the aminal tether can be achieved in a single step under mild conditions to reveal the free diamine. We expect that this work will promote the further use of mixed aminal tethers in organic synthesis. Abstract : Ideal combination : Vicinal diamines with a wide variety of alkynyl, vinyl, aryl, and hetereoaryl groups are obtained with complete regioselectivity and high diastereoselectivity via in situ aminal formation and Pd‐catalyzed carboamination of allyl amines. Key to the reaction is the use of carbamate‐protected trifluoromethyl aldimines in their stable hemiaminal form. Cleavage of the aminal tether was achieved under mild conditions.