An Unusual N-Boc Deprotection of Benzamides under Basic Conditions

For the first time, an unusal cleavage of N‐tert‐butyloxycarbonyl (N‐Boc) protection from N‐Boc‐protected benzamide under basic conditions in excellent yields is reported. The deprotection involves the N‐Boc emigration from the benzamide to form 2‐O‐Boc group followed by O‐Boc deprotection on the phenyl ring.     

A New Method for Selective Deprotection of Anomeric N,O-Dimethylhydroxylamine Promoted by TMSCl

TMSCl was shown to be an efficient reagent for selective deprotection of the anomeric position protected as N,O-dimethylhydroxylamine glycoside. This deprotection condition was proved to be compatible with a number of protecting groups, such as the TBDPS, acetyl, benzyl, benzylidene, and benzoyl groups.     

Selective Deprotection of Fully Benzoylated Nucleoside Derivatives

Abstract

Selective deprotection of benzoylated hydroxyl groups is one of the crucial problems in the synthesis of nucleoside analogues as well as of other polyfunctional molecules.     

Kukhtin–Ramirez-Reaction-Inspired Deprotection of Sulfamidates for the Synthesis of Amino Sugars

Herein, we present a mild strategy for deprotecting cyclic sulfamidates via the Kukhtin–Ramirez reaction to access amino sugars. The method features the removal of the sulfonic group of cyclic sulfamidates, which occurs through an N-H insertion reaction that implicates the Kukhtin–Ramirez adducts, followed by a base-promoted reductive N-S bond cleavage. The mild reaction conditions of the protocol enable the formation of amino alcohols including analogs that bear multiple functional groups.     

Simple and Efficient Method for Deprotection of Tetrahydropyranyl Ethers by Using Silica Supported Sodium Hydrogen Sulphate

Tetrahydropyranyl (THP) ethers have been efficiently and simply deprotected by using Silica supported sodium hydrogen sulphate (NaHSO₄‐SiO₂) in methanol at room temperature to regenerate the parent alcohols in high yields.     

Deprotection of Acetals from Unsaturated,Unstable Bromoketones

The unstable ketones 1-bromo-3-buten-2-one, 1-bromo-3-butyn-2-one, and 1,3-dibromo-3-buten-2-one can be obtained from the corresponding acetals in high yields by treating the acetals with anhydrous iron (III) chloride suspended on dry silica. A simplified procedure for preparing the reagent is also given.     

P4VP-H2SO4-Catalyzed Chemoselective Protection of Aldehydes to Acylal Along with Deprotection Reactions

Poly(4-vinylpyridine)-supported sulfuric acid is an excellent reusable heterogeneous catalyst for the chemoselective synthesis of 1,1-diacetates(acylal) from aldehydes in dichloromethane at room temperature within a few minutes. The protection of salicyaldehyde generated an anhydro-dimer as single product under similar reaction conditions. The catalyst is equally applicable for the deprotection of acylal in acetonitrile. The catalyst was prepared by the wet impregnation technique.     

Mild Approach to the Deprotection of Troc from Protected Amines Using Mischmetal and TMSCl

The 2,2,2-trichloroethoxycarbonyl (Troc) protecting group was efficiently removed from Troc-protected aliphatic and aromatic amines and also some Troc, Tos- and Troc, Ac-protected amines using activated mischmetal (MM). All reactions were performed by refluxing in dry tetrahydrofuran under an argon atmosphere and gave moderate to excellent yields. Several new compounds were synthesized, and new data about reactivity of Troc group were obtained.     

Synthesis and Sequential Deprotection of Triblock Copolypept(o)ides Using Orthogonal Protective Group Chemistry

The synthesis of triblock copolymers based on polysarcosine, poly‐N‐ε‐t‐butyloxycarbonyl‐l ‐lysine, and poly‐N‐ε‐t‐trifluoroacetyl‐l ‐lysine by ring‐opening polymerization of the corresponding α‐amino acid N‐carboxyanhydrides (NCAs) is described. For the synthesis of N‐ε‐t‐butyloxycarbonyl‐l ‐lysine (lysine(Boc)) NCAs, an acid‐free method using trimethylsilylchloride/triethylamine as hydrochloric acid (HCl) scavengers is presented. This approach enables the synthesis of lysine(Boc) NCA of high purity (melting point 138.3 °C) in high yields. For triblock copolypept(o)ides, the degree of polymerization (X_n) of the polysarcosine block is varied between 200 and 600; poly‐N‐ε‐t‐butyloxycarbonyl‐l ‐lysine and poly‐N‐ε‐t‐trifluoroacetyl‐l ‐lysine blocks are designed to have a X_n in the range of 10–50. The polypeptide‐polypeptoid hybrids (polypept(o)ides) can be synthesized with precise control of molecular weight, high end group integrity, and dispersities indices between 1.1 and 1.2. But more important, the use of tert‐butyloxycarbonyl‐ and trifluoroacetyl‐protecting groups allows the selective, orthogonal deprotection of both blocks, which enables further postpolymerization modification reactions in a block‐selective manner. Therefore, the presented synthetic approach provides a versatile pathway to triblock copolypept(o)ides, in which functionalities can be separated in specific blocks.

     

Efficient Chemoselective Mild Deprotection of S,Sand S,O-Acetals and Ketals with Electrophilic Halogens

A novel and simple method for the chemoselective deprotection of S,S- and S,O-acetals and ketals in the presence of their O,O-analogs with electrophilic halogens to their corresponding carbonyl compounds is described using N-bromosuccinimide, N-chlorosuccinimide, 2,4,4,6-tetrabromo-2,5-cyclohexen-1-one, trichlorocyanuric acid, or molecular bromine in aqueous acetonitrile. The use of these reagents in the presence of hydrated silica gel provide efficient, novel, and mild procedures for the deprotection of cyclic and acyclic O,O-, S,S-, and S,O-acetals and ketals in excellent yields in short reaction times.     

Bismuth compounds in organic synthesis. Deprotection of ketoximes using bismuth bromide-bismuth triflate

Ketoximes undergo deprotection in CH₃CN/acetone/H₂O (3:6:1) in the presence of 20-40 mol% BiBr₃/5 mol% Bi(OTf)₃. Bismuth(III) salts are relatively non-toxic, insensitive to air and inexpensive. These features coupled with the use of a relatively non-toxic solvent system make this method an attractive alternative to existing routes for deprotection of ketoximes.     

Preparation,characterization, and properties of polyamic acid nano‐emulsion

A facile method was developed to prepare polyamic acid (PAA) nano‐emulsion using a non‐aqueous emulsification. The resultant PAA nano‐emulsion was characterized by light‐scattering particle size analysis, transmission electron microscopy (TEM), zeta potential, and conductivity analyses. It was found that polyamic acid salt (PAS), formed by partially neutralizing PAA at the carboxylic groups using triethyl amine (TEA), was of great importance for nano‐emulsification. The effect factors on the formation of PAA nano‐emulsion were investigated. To get a stable PAA nano‐emulsion in methanol (precipitant), the following ratios are required: amine/COOH (molar ratio) = 0.6–0.7, precipitant/solvent (mass ratio) = 1.5–2.25. A PAA nano‐emulsion with droplets ranging in size from 50 to 100 nm was obtained under optimized conditions. The driving force for the formation of PAA nano‐emulsion was also discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Heterogeneous Thiocyanation of Benzylic Alcohols and Silyl and THP Ethers,and Deprotection of Silyl and THP-Ethers by [PCl3-n(SiO2)n] (Silphos)

Silicaphosphite (silphos), [PCl_3-n(SiO₂)_n], as a heterogeneous phosphorous compound, catalyzes the thiocyanation of benzylic alcohols and silyl and THP ethers in the presence of I₂ and NH₄SCN in refluxing CH₃CN. The produced silphos oxide byproduct can be easily separated by a simple filtration. Silphos is also used for the efficient and selective deprotection of silyl and THP-ethers to their corresponding alcohols.