Abstract
According to the earlier published synthesis of the C‐terminal nonapeptide of Trichovirin I 1B, Z‐Ser(^t^Bu)‐Val‐Aib‐Pro‐Aib‐Leu‐Aib‐Pro‐Leuol (5), the complete tetradecapeptide Z‐Aib‐Asn(Trt)‐Leu‐Aib‐Pro‐Ser(^t^Bu)‐Val‐Aib‐Pro‐Aib‐Leu‐Aib‐Pro‐Leuol (11b), a protected Trichovirin I 1B, has now been prepared by means of the ‘azirine/oxazolone method’. With the exception of the N‐terminal Aib(1), all Aib residues were introduced by the coupling of the corresponding amino or peptide acids with 2,2‐dimethyl‐2__H__‐azirine‐3‐(N‐methyl‐N‐phenylamine) (1a) and methyl N‐(2,2‐dimethyl‐2__H__‐azirin‐3‐yl)‐L‐prolinate (3a) as the Aib and Aib‐Pro synthons, respectively. Single crystals of two segments, i.e., the N‐terminal hexapeptide Z‐Aib‐Asn(Trt)‐Leu‐Aib‐Pro‐Ser(^t^Bu)‐OMe (23) and the C‐terminal octapeptide Z‐Val‐Aib‐Pro‐Aib‐Leu‐Aib‐Pro‐Leuol (17), were obtained and their structures have been established by X‐ray crystallography. Following the same strategy, the C‐terminal nonapeptide of Trichovirin I 4A, Z‐Ala‐Val‐Aib‐Pro‐Aib‐Leu‐Aib‐Pro‐Leuol (26), was also synthesized and characterized by X‐ray crystallography.