Synthesis of 9-fluorenylmethyl esters using 9-fluorenylmethylchloroformate

Merette, Sandrine; Burd, Andrew; Deadman, John

doi:10.1016/s0040-4039(98)02364-8

Cited by 19 publications

(11 citation statements)

References 7 publications

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“…The latter method is also used for the preparation of Fm esters 118, 119. Alternatively, these esters can be obtained from 9‐fluorenylmethylchloroformate in the presence of DIEA/DMAP120 or by transesterification of p ‐nitrophenyl esters in the presence of imidazole 121…”

Section: C‐terminal Carboxyl Protecting Groupsmentioning

confidence: 99%

Orthogonal protecting groups forNα-amino andC-terminal carboxyl functions in solid-phase peptide synthesis

Alberício¹

2000

Biopolymers

108

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For the controlled synthesis of even the simplest dipeptide, the Nα‐amino group of one of the amino acids and the C‐terminal carboxyl group of the other should both be blocked with suitable protecting groups. Formation of the desired amide bond can now occur upon activation of the free carboxyl group. After coupling, peptide synthesis can be continued by removal of either of the two protecting groups and coupling with the free C‐terminus or Nα‐amino group of another protected amino acid. When three functional amino acids are present in the sequence, the side chain of these residues also has to be protected. It is important that there is a high degree of compatibility between the different types of protecting groups such that one type may be removed selectively in the presence of the others. At the end of the synthesis, the protecting groups must be removed to give the desired peptide. Thus, it is clear that the protection scheme adopted is of the utmost importance and makes the difference between success and failure in a given synthesis. Since R. B. Merrifield introduced the solid‐phase strategy for the synthesis of peptides, this prerequisite has been readily accepted. This strategy is usually carried out using two main protection schemes: the tert‐butoxycarbonyl/benzyl and the 9‐flourenylmethoxycarbonyl/tert‐butyl methods. However, for the solid‐phase preparation of complex or fragile peptides, as well as for the construction of libraries of peptides or small molecules using a combinatorial approach, a range of other protecting groups is also needed. This review summarizes other protecting groups for both the Nα‐amino and C‐terminal carboxyl functions. © 2000 John Wiley & Sons, Inc. Biopoly 55: 123–139, 2000

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Section: C‐terminal Carboxyl Protecting Groupsmentioning

confidence: 99%

Orthogonal protecting groups forNα-amino andC-terminal carboxyl functions in solid-phase peptide synthesis

Alberício¹

2000

Biopolymers

108

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“…The latter was synthesized starting from the known Boc-Phe-OFM [27] which, after removal of the Boc group from its N-terminus, was first acylated with Chpca(MOM)-OH (10) and then O-MOM-deprotected to furnish the acylamino acid 23 in 82 % yield over three steps. Finally, the HATU-mediated acylation of H-(NO 2 )Nle-Phe-Val-OMe with Chba-OH (3-chloro-2-hydroxybenzoic acid) yielded 21e in 45 % yield.…”

Section: Substance Fedmentioning

confidence: 99%

“…[3b] HOAt, [31] Chpca(MOM)-OH (10), [9] racemic (2-nitrophenyl)alanine (18), [16] Boc-Phe-Val-OMe (19), [21] Boc-Phe-OFM (22), [27] Chpca(MOM)-(3-Ncp)Ala-OFM (24), [9] PyAOP [31] were prepared as described previously elsewhere. Feeding experiments and biological assays were carried out as described elsewhere.…”

Section: Generalmentioning

confidence: 99%

Synthesis and Precursor‐Directed Biosynthesis of New Hormaomycin Analogues

et al. 2006

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Several new analogues of hormaomycin (1), a peptide lactone with interesting biological activities, were prepared by total synthesis or by precursor‐directed biosynthesis. The new analogues 2a–c, 3a–c, O‐MOM‐1 and epi‐O‐MOM‐1 as well as the model acyl tripeptides 20a–c and 21a–e were tested for their antibiotic activities to give new insights into structure–activity relationships of this class of compounds. In this context, an unexpected activity of 2c against C. albicans was discovered. The precursors necessary for feeding experiments, the amino acids 14a, 14b and 17, were prepared in 31, 48 and 55 % yield over 4 and 3 steps, respectively. In addition, these studies provided some new information about the biosynthetic route to furnish compound 1. They also support the notion that the combination of chemical and biological methods may provide a broad range of analogues of an interesting biologically active natural product. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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“…Hydrolysis of the nitrile group in the intermediate 105 according to protocol Cacchi et al [103] led to the amide 106 (all attempts to hydrolyze 105 or 106 were unsuccessful) which, in turn, was doubly acylated with Boc 2 O to give the desired triacylated intermediate 107 together with the side product 108. The alkaline hydrolysis of 107 [104] Phenylalanine 9-fluorenylmethyl ester 111 obtained after Boc-group removal from N-termini of N-Boc protected amino ester 110 [105] with 5 M HCl in Et 2 O was coupled with the acid 109 using the combination of N'-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDC) and 1-hydroxybenzotriazole (HOBt) to give the acyl amino ester 112 in 93% yield, which after removal of the methoxymethyl group with MgBr 2 ⋅Et 2 O and ethyl mercaptan in diethyl ether [106] gave the ester 113 (88%). The latter was deprotected using 20% diethylamine in CH 2 Cl 2 to give the unstable 114 in 100% crude yield, which was immediately coupled with the dipeptide 118 obtained after deprotection of the peptide 117 with 5 M HCl in Et 2 O, which was previously prepared from N-Boc protected phenylalanine 115 and valine methyl ester 116 using dicyclohexylcarbodiimide (DCC) and HOBt in 82% yield, using the O-(7-azabenzotriazole-1yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU) [107] to give the desired acyltripeptide 119 in 23% yield.…”

Section: Scheme 28mentioning

confidence: 99%

“…(2S,4R)-4-Tosyloxi-N-Boc-proline, [22] tert-butyl (R)-N-(tert-butyloxycarbonyl)pyroglutamate [as it was described for (S)-isomer], [34] tert-butyl (2R,4R)-(N-tert-butyloxycarbonyl)-4-allylpyroglutamate [as it was described for (2S,4S)-isomer], [35] methyl (2S,4R)-(N-tertbutyloxycarbonyl)-4-hydroxyprolinate, [46] methyl (2S,4RS)-(N-tert-butyloxycarbonyl)-4iodopro-linate, [47] (2S,4R)-(N-tert-butyloxycarbonyl)-4-hydroxyproline, [53] , (2S,4R)-(N-tertbutyloxy-carbonyl)-4-mesyloxyprolinol, [57] (2S,4R)-(N-tert-butyloxycarbonyl)-4-hydroxyprolixnol tert-butyldimetylsilyl ester, [62] adduct of (2S,4R)-4-hydroxyproline and pivalic aldehyde, [64] rac-(trans-2'-nitrocyclopropyl)methanol, [84] (1,1-dideutero)ethyltriphenylphosphonium bromide, [72] (R)-allo-threonine, [75] (4R)-phenyloxazolidinone-2, [80] (4R)-4-phenyl-3-(3'phenylbutyryl)oxazo-lidinone-2, [79] (4R,3'S)-4-phenyl-3-(3'-phenylbutyryl)oxazolidinone-2 [as it was described for (4S,3'R)-isomer], [81] 1,1,3,3-tetramethyl guanidinium azide, [136] rac-βmethylphenylalanine, [137] (2S,3R)-β-methylphenylalanine, [79] (S) and (R) Belokon's chiral glycine equivalents, [86] (4R)-4-isopropyl-1,3-trans-(2'-nitrocyclopropyl)carbonyloxazolidinones-2, [14] trans-(2'-nitrocyclopro-pyl)methyl iodide, [80] 1-methoxysuccinimide, [97] 2-amino-6chloropyridine, [99] 2-acetamido-6-chloropyridine, [101] 2,6-dichloropyridine-N-oxide, [102] 9flourenylmethyl (S)-(N-tert-butyloxycarbonyl)phenylalaninate, [105] 2-acetamino-6-aminopyridine, [107] (S)-(2-nitrophenyl)sulfenylproline, [116] (S)-(2-nitrophenyl)sulfenylisoleucine, [116] methyl (N-tert-butyloxycarbonyl)-isoleucyl-prolinate, [117] p-nitrobenzyl (R)-allo-(N-tert-butyloxycarbonyl)threoninate [as it was described for (S)-threo-isomer], [120] (2S,3R)-(N-9-fluorenylmethyloxycarbonyl)-β-methylphenylalanine, …”

Section: Compoundmentioning

confidence: 99%

Final Elucidation of the Absolute Configuration of Hormaomycin - Total Synthesis of Hormaomycin and Analogs

Zlatopolski¹

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Synthesis of 9-fluorenylmethyl esters using 9-fluorenylmethylchloroformate

Cited by 19 publications

References 7 publications

Orthogonal protecting groups forNα-amino andC-terminal carboxyl functions in solid-phase peptide synthesis

Orthogonal protecting groups forNα-amino andC-terminal carboxyl functions in solid-phase peptide synthesis

Synthesis and Precursor‐Directed Biosynthesis of New Hormaomycin Analogues

Final Elucidation of the Absolute Configuration of Hormaomycin - Total Synthesis of Hormaomycin and Analogs

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