Adamantyloxycarbonyl, a New Blocking Group. Preparation of 1-Adamantyl Chloroformate<sup>1</sup>

Haas, Winfried; Krumkalns, Eriks V.; Gerzon, Koert

doi:10.1021/ja00961a024

Cited by 66 publications

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“…The increased stability of the neat substance [35] could be due in part to it being a solid and in part due to alkene formation, which would put a double bond at a bridgehead, being highly unfavorable (Bredt’s rule) relative to the dominant alkene-formation pathway involved in the tert -butyl chloroformate decomposition.…”

Section: Introductionmentioning

confidence: 99%

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

et al. 2012

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The “parent” tertiary alkyl chloroformate, tert-butyl chloroformate, is unstable, but the tert-butyl chlorothioformate (1) is of increased stability and a kinetic investigation of the solvolyses is presented. Analyses in terms of the simple and extended Grunwald-Winstein equations are carried out. The original one-term equation satisfactorily correlates the data with a sensitivity towards changes in solvent ionizing power of 0.73 ±0.03. When the two-term equation is applied, the sensitivity towards changes in solvent nucleophilicity of 0.13 ± 0.09 is associated with a high (0.17) probability that the term that it governs is not statistically significant.

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Section: Introductionmentioning

confidence: 99%

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

et al. 2012

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“…The procedure for converting the secondary amine in to the carbamoyl chloride was closely related to that used previously 22 for converting 1-adamantanol into the chloroformate.…”

Section: Discussionmentioning

confidence: 99%

Solvolysis-decomposition ofN-1-adamantyl-N-p-tolylcarbamoyl chloride in hydroxylic solvents

Kevill

Upadhyay

1997

J. Phys. Org. Chem.

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In hydroxylic solvents, N-1-adamantyl-N-p-tolylcarbamoyl chloride undergoes a facile rate-determing ionization with very little assistance from nucleophilic solvation (very low sensitivity to changes in solvent nucleophilicity). In the relatively nucleophilic aqueous ethanol or aqueous acetone, the cation formed reacts directly with the solvent. In fluoroalcohols, the low nucleophilicity of the solvent allows an effective competition from a pathway involving disproportionation to the 1-adamantyl cation and p-tolyl isocyanate, followed by reaction of the new cation either with solvent or with the chloride ion formed in the initial ionization. Grunwald-Winstein plots against Y C1 values show for different binary solvent systems a marked dispersion, which can be considerably reduced by incorporation into the analyses of a term governed by the aromatic ring parameter. (I).

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“…Many other urethane type N a -protecting groups have been used in solution synthesis, such as the tert-amyloxycarbonyl (Aoc) group 16, which is removed by TFA [68][69][70][71], and the 1-adamantyloxycarbonyl (1-Adoc) group 17 [72] as well, although neither have been extensively applied in peptide synthesis.…”

Section: + +mentioning

confidence: 99%

Solution‐Phase Peptide Synthesis

Tsuda

Okada

2010

Amino Acids, Peptides and Proteins in Organic Chemistry

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Adamantyloxycarbonyl, a New Blocking Group. Preparation of 1-Adamantyl Chloroformate¹

Cited by 66 publications

References 0 publications

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

Solvolysis-decomposition ofN-1-adamantyl-N-p-tolylcarbamoyl chloride in hydroxylic solvents

Solution‐Phase Peptide Synthesis

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Adamantyloxycarbonyl, a New Blocking Group. Preparation of 1-Adamantyl Chloroformate1

Cited by 66 publications

References 0 publications

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

Solvolysis-decomposition ofN-1-adamantyl-N-p-tolylcarbamoyl chloride in hydroxylic solvents

Solution‐Phase Peptide Synthesis

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Adamantyloxycarbonyl, a New Blocking Group. Preparation of 1-Adamantyl Chloroformate¹