VCD Analysis of Axial Chirality in Synthetic Stereoisomeric Biaryl-Type bis-Isochroman Heterodimers with Isolated Blocks of Central and Axial Chirality

Author:

Czenke Zoltán12,Mándi Attila1ORCID,Király Sándor Balázs1ORCID,Kiss-Szikszai Attila1ORCID,Kónya-Ábrahám Anita1,Kurucz-Szabados Anna12,Cserepes Krisztián12,Bényei Attila3ORCID,Zhang Changsheng4ORCID,Kicsák Máté1ORCID,Kurtán Tibor1ORCID

Affiliation:

1. Department of Organic Chemistry, University of Debrecen, P. O. Box 400, 4002 Debrecen, Hungary

2. Doctoral School of Chemistry, University of Debrecen, Egyetem tér 1., 4032 Debrecen, Hungary

3. Department of Physical Chemistry, University of Debrecen, Egyetem tér 1., 4032 Debrecen, Hungary

4. Key Laboratory of Tropical Marine Bio-Resources and Ecology, Guangdong Key Laboratory of Marine Materia Medica, Institutions of South China Sea Ecology and Environmental Engineering, South China Sea Institute of Oceanology, Chinese Academy of Sciences, Guangzhou 510301, China

Abstract

Optically active heterodimeric 5,5′-linked bis-isochromans, containing a stereogenic ortho-trisubstituted biaryl axis and up to four chirality centers, were synthesized stereoselectively by using a Suzuki–Miyaura biaryl coupling reaction of optically active isochroman and 1-arylpropan-2-ol derivatives, providing the first access to synthetic biaryl-type isochroman dimers. Enantiomeric pairs and stereoisomers up to seven derivatives were prepared with four different substitution patterns, which enabled us to test how OR, ECD, and VCD measurements and DFT calculations can be used to determine parallel central and axial chirality elements in three isolated blocks of chirality. In contrast to natural penicisteckins A–D and related biaryls, the ECD spectra and OR data of (aS) and (aR) atropodiastereomers did not reflect the opposite axial chirality, but they were characteristic of the central chirality. The atropodiastereomers showed consistently near-mirror-image VCD curves, allowing the determination of axial chirality with the aid of DFT calculation or by comparison of characteristic VCD transitions.

Funder

National Research, Development and Innovation Office

National Research, Development and Innovation Fund of Hungary

Publisher

MDPI AG

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