Highly enantioselective enone epoxidation catalyzed by short solid phase-bound peptides: Dominant role of peptide helicity

被引：97

作者：

Berkessel, A ^{[1
]}

Gasch, N ^{[1
]}

Glaubitz, K ^{[1
]}

Koch, C ^{[1
]}

机构：

[1] Univ Cologne, Inst Organ Chem, D-50939 Cologne, Germany

来源：

ORGANIC LETTERS | 2001年 / 3卷 / 24期

关键词：

D O I：

10.1021/ol0166451

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] The series of L-Leu 1-20-mers, peptides carrying 1-5 N-terminal Gly residues, and oligomers of (S)-ss (3)-Leu and (1R,2R)-2-aminocyclohexane-carboxylic acid were synthesized on TentaGel S NH2. Five L-Leu residues were found sufficient to catalyze the Julia-Colonna epoxidation of chalcone with 96-98% ee. Experiment and molecular modeling suggest that catalysis is effected by binding of the enone to the N-terminus, and the helicity of the peptide determines the epoxide configuration through face-selective delivery of a hydroperoxide anion.

引用

页码：3839 / 3842

页数：4

共 20 条

[1] Polyamino acid-catalysed asymmetric epoxidation: Sodium percarbonate as a source of base and oxidant
Allen, JV
Drauz, KH
Flood, RW
Roberts, SM
Skidmore, J
[J]. TETRAHEDRON LETTERS, 1999, 40 (29) : 5417 - 5420
[2] [Anonymous], 2012, Introduction to protein structure
[3] Synthesis and characterization of trans-2-aminocyclohexanecarboxylic acid oligomers:: An unnatural helical secondary structure and implications for β-peptide tertiary structure
Appella, DH
Christianson, LA
Karle, IL
Powell, DR
Gellman, SH
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (26) : 6206 - 6212
[4] Towards a mechanistic insight into the Julia-Colonna asymmetric epoxidation of α, β-unsaturated ketones using discrete lengths of poly-leucine.
Bentley, PA
Cappi, MW
Flood, RW
Roberts, SM
Smith, JA
[J]. TETRAHEDRON LETTERS, 1998, 39 (50) : 9297 - 9300
[5] Asymmetric epoxidation of enones employing polymeric alpha-amino acids in non-aqueous media
Bentley, PA
Bergeron, S
Cappi, MW
Hibbs, DE
Hursthouse, MB
Nugent, TC
Pulido, R
Roberts, SM
Wu, LE
[J]. CHEMICAL COMMUNICATIONS, 1997, (08) : 739 - 740
[6] The effect of the primary structure of the polypeptide catalyst on the enantioselectivity of the Julia-Colonna asymmetric epoxidation of enones
Bentley, PA
Flood, RW
Roberts, SM
Skidmore, J
Smith, CB
Smith, JA
[J]. CHEMICAL COMMUNICATIONS, 2001, (17) : 1616 - 1617
[7] Stereocontrolled ring-opening of some enantiomerically enriched epoxy ketones and epoxy alcohols using trimethylaluminium:: synthesis of (S)-2-arylpropanoic acids
Carde, L
Davies, DH
Roberts, SM
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 2000, (15): : 2455 - 2463
[8] Efficient asymmetric epoxidation of α,β-unsaturated ketones using a soluble triblock polyethylene glycol-polyamino acid catalyst
Flood, RW
Geller, TP
Petty, SA
Roberts, SM
Skidmore, J
Volk, M
[J]. ORGANIC LETTERS, 2001, 3 (05) : 683 - 686
[9] Foldamers: A manifesto
Gellman, SH
[J]. ACCOUNTS OF CHEMICAL RESEARCH, 1998, 31 (04) : 173 - 180
[10] Preparation of N-Fmoc-protected β2- and β3-amino acids and their use as building blocks for the solid-phase synthesis of β-peptides
Guichard, G
Abele, S
Seebach, D
[J]. HELVETICA CHIMICA ACTA, 1998, 81 (02) : 187 - 206

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