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Volumn 74, Issue 4, 2009, Pages 1440-1449

Synthesis and Characterization of Nitroaromatic Peptoids: Fine Tuning Peptoid Secondary Structure through Monomer Position and Functionality

Author keywords

[No Author keywords available]

Indexed keywords

A-PRIORI; BIOMOLECULAR INTERACTIONS; BUILDING BLOCKS; CHIRAL AMINES; CIRCULAR DICHROISMS; ELECTRON DEFICIENTS; FINE TUNING; FOLDAMERS; FOLDING PROCESS; INTRAMOLECULAR HYDROGEN BONDS; LOOP STRUCTURES; MONOMER UNITS; N TERMINALS; NEW APPROACHES; NONAMERS; PEPTOIDS; SECONDARY STRUCTURES; SIDE CHAINS; SIDE-CHAIN STRUCTURES; SINGLE MONOMERS; SOLID-PHASE; STERIC INTERACTIONS; SYNTHESIS AND CHARACTERIZATIONS; SYNTHESIS TECHNIQUES; SYSTEMATIC STUDIES; TERMINAL POSITIONS; THERAPEUTIC AGENTS;

EID: 64349123897     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo8023363     Document Type: Article
Times cited : (44)

References (36)
  • 26
    • 64349123769 scopus 로고    scopus 로고
    • We also were able to synthesize s2ne (5b) from 2′-nitroacetophenone via a selective reduction of the ketone to the R-alcohol, conversion to the S-azide, and reduction to the S-amine, similar to the work of Gorske et al, see ref 16, However, the overall yield of 5b was significantly lower using this approach 12, data not shown
    • We also were able to synthesize s2ne (5b) from 2′-nitroacetophenone via a selective reduction of the ketone to the R-alcohol, conversion to the S-azide, and reduction to the S-amine, similar to the work of Gorske et al. (see ref 16). However, the overall yield of 5b was significantly lower using this approach (12%, data not shown).
  • 29
    • 84869269838 scopus 로고    scopus 로고
    • 1H NMR (>95%) and HPLC (96% purity at 220 nm).
    • 1H NMR (>95%) and HPLC (96% purity at 220 nm).
  • 30
    • 84869269839 scopus 로고    scopus 로고
    • We synthesized and characterized an o-methyl analogue of peptoid 9 as a steric control. As (S)-1-(2-methylphenyl)ethylamine was not commercially available, we utilized 2-methylbenzylamine (2mb) for this control peptoid (V2mb(Vspe)8, The removal of the α-methyl group on the N-terminal side chain in this peptoid (and in similar nonamers we have studied) appears to strengthen the threaded loop (data not shown, We believe this may be due to an electronic effect, as the lack of an α-methyl group should decrease electron density at the N-terminal ammonium. Since we were unable to make direct comparisons between the control N2mb(Nspe)8 and peptoid 9, we omit this relatively complex analysis here for brevity
    • We synthesized and characterized an o-methyl analogue of peptoid 9 as a steric control. As (S)-1-(2-methylphenyl)ethylamine was not commercially available, we utilized 2-methylbenzylamine (2mb) for this control peptoid (V2mb(Vspe)8). The removal of the α-methyl group on the N-terminal side chain in this peptoid (and in similar nonamers we have studied) appears to strengthen the threaded loop (data not shown). We believe this may be due to an electronic effect, as the lack of an α-methyl group should decrease electron density at the N-terminal ammonium. Since we were unable to make direct comparisons between the control N2mb(Nspe)8 and peptoid 9, we omit this relatively complex analysis here for brevity.
  • 31
    • 64349108878 scopus 로고    scopus 로고
    • We note that DMSO may be able to disrupt hydrogen bonding in a threaded loop-type structure based on a qualitative comparison of the NMR spectra of 2 in acetonitrile-d3 and DMSO-d6; see the Supporting Information, Therefore, the cis/trans ratio determined for 7 may be higher in DMSO relative to acetonitrile. We include the DMSO-d3 data here to provide our most comprehensive analysis of peptoid 7
    • 3 data here to provide our most comprehensive analysis of peptoid 7.
  • 32
    • 64349106925 scopus 로고    scopus 로고
    • Similar blue shifts in CD spectra for peptoids containing Nsnp residues have been observed previously; see ref 7a
    • Similar blue shifts in CD spectra for peptoids containing Nsnp residues have been observed previously; see ref 7a.
  • 33
    • 64349115653 scopus 로고    scopus 로고
    • For a space-filling model of the threaded loop structure adopted by nonamer 2, see Figure 4 in ref 10.
    • For a space-filling model of the threaded loop structure adopted by nonamer 2, see Figure 4 in ref 10.
  • 34
    • 64349101187 scopus 로고    scopus 로고
    • Assignments in the 1D 1H NMR spectrum for 9 were corroborated by 2D NOESYdata. See theSupporting Informationforthe 1D1HNMRspectrum of peptoid 9.
    • Assignments in the 1D 1H NMR spectrum for 9 were corroborated by 2D NOESYdata. See theSupporting Informationforthe 1D1HNMRspectrum of peptoid 9.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.