Premium
Vibrational circular dichroism as a probe of solid‐state organisation of derivatives of cyclic β‐amino acids: Cis ‐ and trans ‐2‐aminocyclobutane‐1‐carboxylic acid
Author(s) -
Declerck Valérie,
PérezMellor Ariel,
Guillot Régis,
Aitken David J.,
Mons Michel,
Zehnacker Anne
Publication year - 2019
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.23083
Subject(s) - chemistry , vibrational circular dichroism , hydrogen bond , circular dichroism , infrared spectroscopy , monomer , spectroscopy , intermolecular force , crystallography , computational chemistry , stereochemistry , molecule , organic chemistry , polymer , physics , quantum mechanics
Peptide models built from cis ‐ and trans ‐2‐aminocyclobutane‐1‐carboxylic acids (ACBCs) are studied in the solid phase by combining Fourier‐transform infrared spectroscopy (FTIR) absorption spectroscopy, vibrational circular dichroism (VCD), and quantum chemical calculations using density functional theory (DFT). The studied systems are N‐ tert ‐butyloxycarbonyl (Boc) derivatives of 2‐aminocyclobutanecarboxylic acid (ACBC) benzylamides, namely Boc−( cis ‐ACBC)−NH−Bn and Boc−( trans ‐ACBC)−NH−Bn. These two diastereomers show very different VCD signatures and intensities, which of the trans ‐ACBC derivative being one order of magnitude larger in the region of the ν (CO) stretch. The spectral signature of the cis ‐ACBC derivative is satisfactorily reproduced by that of the monomer extracted from the solid‐state geometry of related ACBC derivatives, which shows that no long‐range effects are implicated for this system. In terms of hydrogen bonds, the geometry of this monomer is intermediate between the C6 and C8 structures (exhibiting a 6‐ or 8‐membered cyclic NH⋯O hydrogen bond) previously evidenced in the gas phase. The benzyl group must be in an extended geometry to reproduce satisfactorily the shape of the VCD spectrum in the ν (CO) range, which qualifies VCD as a potential probe of dispersion interaction. In contrast, reproducing the IR and VCD spectrum of the trans ‐ACBC derivative requires clusters larger than four units, exhibiting strong intermolecular H‐bonding patterns. A qualitative agreement is obtained for a tetramer, although the intensity enhancement is not reproduced. These results underline the sensitivity of VCD to the long‐range organisation in the crystal.