Design of Chiral Bis-phosphoric Acid Catalyst Derived from (R)-3,3 '-Di(2-hydroxy-3-arylphenyl)binaphthol: Catalytic Enantioselective Diels-Alder Reaction of alpha,beta-Unsaturated Aldehydes with Amidodienes

作者：Momiyama Norie^*; Konno Tohru; Furiya Yuichi; Iwamoto Takeaki; Terada Masahiro

来源：Journal of the American Chemical Society, 2011, 133(48): 19294-19297.

DOI：10.1021/ja2081444

Chiral bis-phosphoric acid 1 was designed to identify a new class of structural features in chiral Bronsted acid catalysts. X-ray diffraction analysis revealed the single atropisomer 1, bearing S axial chirality at 3,3'-biaryl substituents on (R)-binaphthyl and intramolecular hydrogen bonding between the two phosphoric acid moieties. The newly designed his-phosphoric acid 1 was evaluated in the Diels-Alder reaction of alpha,beta-unsaturated aldehydes 4 with 1-N-acylamino-1,3-butadienes 3. After systematic variation of the catalyst substituents, as well as the N-acyl substituents of 1,3-butadiene, the use of an N-Cbz amidodiene 3a in the presence of bis-phosphoric acid le with a 2,4,6-tri-isopropylphenyl group was found to be optimal to yield the 1S,6R enantiomeric product 5aa in a Diels-Alder reaction of acrolein (4a). Application of this method to substituted substrates was found to be an efficient approach to the enantioselective synthesis of 3- and 3,6-substituted cyclic formylcarbamates 5. The specific character as well as the utility of le was further established by comparing its enantioselectivity, absolute stereochemistry, and catalytic efficiency with those of mono-phosphoric acid 2.

• 出版日期2011-12-7