Complementary double‐stranded helical oligomers bearing achiral bifunctional groups that catalyze asymmetric aldol reaction. Issue 3 (10th January 2020)

• Record Type: Journal Article
• Authors: Taura, Daisuke; Shimomura, Kouhei; Ousaka, Naoki; Yashima, Eiji
• Is Part Of: Chirality. Volume 32:Issue 3(2020)
• Page Start: 254
• Page End: 264
• Publication Date: 2020-01-10
• Subjects: aldol reaction -- complementary double helix -- enantioselectivity -- salt bridge -- supramolecular catalysis; Chirality -- Periodicals; Pharmaceutical chemistry -- Periodicals; 541.22
• DOI: 10.1002/chir.23169
• Languages: English
• ISSNs: 0899-0042

Abstract

Abstract: Two novel chiral dimer and trimer strands composed of m ‐terphenyl groups linked through p ‐diethynylbenzene units with the chiral amidine group and achiral piperazine group introduced at the terminus or center of the strands, respectively, and its complementary achiral carboxylic acid dimer and trimer were synthesized. The complementary chiral/achiral strands form an excess‐handed double‐helical structure as supported by intense split‐type Cotton effects in the absorption regions of the conjugated backbones biased by the chiral amidinium–carboxylate salt bridges. The double‐helical trimer was found to catalyze the direct aldol reaction of cyclohexanone with 4‐nitrobenzaldehyde and produce the products with a moderate enantioselectivity despite the fact that the catalytically active bifunctional piperazine/carboxylic acid pair introduced in the middle is achiral, indicating the key role of the one‐handed double‐helical framework for supramolecular bifunctional organocatalysis. Abstract :