Wydział Chemii

Qun Zhao

Guangchen Li

Pradeep Nareddy

Frank Jordan

Roger Lalancette

Roman Szostak

Michal Szostak

2022

Angewandte Chemie - International Edition

61

e202207346/1-e202207346/6

10.1002/anie.202207346

Naukowa

Angielski

Artykuł

Amide bond replacement with planar isosteric chalcogen analogues has an important implication for the properties of the N−C(X) linkage in structural chemistry, biochemistry and organic synthesis. Herein, we report the first higher chalcogen derivatives of non-planar twisted amides. The synthesis of twisted thioamide in a versatile system has been accomplished by direct thionation without cleavage of the σ N−C bond. The synthesis of twisted selenoamide has been accomplished by selenation with Woollins’ reagent. The structures of higher chalcogen analogues of non-planar amides were unambiguously confirmed by X-ray crystallography. Reactivity studies were conducted to determine the effect of isologous N−C(O) to N−C(X) replacement on the properties of the amide linkage. Computational studies were employed to evaluate structural and energetic parameters of amide bond alteration in higher chalcogen amides. The study provides the first experimental evidence on the effect of chalcogen isologues on the structural and electronic properties of the non-planar amide N−C(X) linkage.

Amides, Bond Lengths, Conformational Analysis, Structure Elucidation, Winkler–Dunitz Parameters

http://dx.doi.org/10.1002/anie.202207346

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