TY - JOUR
T1 - Total synthesis and structure elucidation of JBIR-39
T2 - A linear hexapeptide possessing piperazic acid and γ-hydroxypiperazic acid residues
AU - Yoshida, Masahito
AU - Sekioka, Naoki
AU - Izumikawa, Miho
AU - Kozone, Ikuko
AU - Takagi, Motoki
AU - Shin-ya, Kazuo
AU - Doi, Takayuki
N1 - Publisher Copyright:
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA.
PY - 2015/2/9
Y1 - 2015/2/9
N2 - The total synthesis and stereochemical structural elucidation of JBIR-39, containing four nonproteinogenic piperazic acid (Piz) residues, is reported. The synthesis includes Sc(OTf)3-catalyzed acylation of a Piz(γ-OTBS) derivative with piperazic acid chloride, providing the desired Piz-Piz(γ-OTBS) dipeptide in high yield without epimerization. After assembling two additional Piz moieties and (S)-isoleucic acid at the N-terminus, amidation with the (R)-α-methylserine ester at the C-terminus, and deprotection afforded the desired (2R,8S)-hexapeptide, which is the assumed structure of JBIR-39. Although the spectral data of the (2R,8 S)-hexapeptide was not identical to JBIR-39, further synthesis of three stereoisomers confirmed the stereochemical structure of JBIR- 39 to be (2S,6S,8S,11 R,16S,21R,26S,27S).
AB - The total synthesis and stereochemical structural elucidation of JBIR-39, containing four nonproteinogenic piperazic acid (Piz) residues, is reported. The synthesis includes Sc(OTf)3-catalyzed acylation of a Piz(γ-OTBS) derivative with piperazic acid chloride, providing the desired Piz-Piz(γ-OTBS) dipeptide in high yield without epimerization. After assembling two additional Piz moieties and (S)-isoleucic acid at the N-terminus, amidation with the (R)-α-methylserine ester at the C-terminus, and deprotection afforded the desired (2R,8S)-hexapeptide, which is the assumed structure of JBIR-39. Although the spectral data of the (2R,8 S)-hexapeptide was not identical to JBIR-39, further synthesis of three stereoisomers confirmed the stereochemical structure of JBIR- 39 to be (2S,6S,8S,11 R,16S,21R,26S,27S).
KW - Acylation
KW - Configuration determination
KW - Natural products
KW - Peptides
KW - Total synthesis
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U2 - 10.1002/chem.201406020
DO - 10.1002/chem.201406020
M3 - Article
C2 - 25524716
AN - SCOPUS:84921877343
VL - 21
SP - 3031
EP - 3041
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 7
ER -