Synthesis of 2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-3-((dimethylamino)methyl)camphor organocatalysts

• Published in: Chirality (New York, N.Y.) Vol. 24; no. 5; pp. 412 - 419
• Main Authors: Grošelj, Uroš, Ričko, Sebastjan, Svete, Jurij, Stanovnik, Branko
• Format: Journal Article
• Language: English
• Published: Chichester, UK John Wiley & Sons, Ltd 01.05.2012
• Subjects: 2,3‐functionalized camphor derivatives; 3-functionalized camphor derivatives; camphor-derived amines; enaminone methodology; enaminone reduction; oxime reduction
• ISSN: 0899-0042; 1520-636X
• DOI: 10.1002/chir.22035

In a stereo‐divergent synthesis, three novel camphor‐derived bifunctional thiourea organocatalysts 7, 8, 9 have been prepared in five steps starting from (+)‐camphor. In addition, borneol‐derived bifunctional thiourea organocatalysts 19/19’ have been prepared in three steps from (1S)‐(+)‐camphorquinone. Novel organocatalysts 7, 8, 9, 19/19’ have been evaluated in a model reaction of Michael addition of dimethyl malonate to trans‐β‐nitrostyrene with low to moderate enantioselectivities (20%–60% ee). Configuration of all novel compounds has been meticulously determined using nuclear magnetic resonance (NMR) techniques. Chirality 24:412–419, 2012. © 2012 Wiley Periodicals, Inc.