Catalyst-free alcoholysis of phosphane-boranes: a smooth, cheap, and efficient deprotection procedure

Catalyst-free alcoholytic deprotection of borane-protected phosphorus compounds offers a smooth, efficient, and clean alternative to existing deprotection methods. In this paper we report our results on the general applicability of deprotecting phosphane- and phosphite-borane adducts by means of simple alcoholysis without the use of molecular sieves as a catalyst. Phosphane-boranes bearing at least one aromatic substituent are readily deprotected in high yields. Borane complexes of trialkylphosphanes or phosphites, however, cannot be deprotected in this way. The main merit of our method is its simplicity: apart from evaporation of the solvent, no further work-up or purification is needed.     

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.     

Synthesis of a cholesterol-appended Tb-DTPA complex by combined removal of tert-Butyl protecting groups and complexation of terbium(III)

The Tb(III)-complex of a cholesterol-DTPA conjugate was prepared in a one-step procedure from the tert-Butyl-protected form of the ligand through reaction with TbCl₃^.6H₂O and NaI in refluxing acetonitrile. The acid-labile carbamate linker that connects the chelating DTPA moiety with the cholesterol unit of the ligand stays intact under these conditions. The combination of deprotection of the ligand with terbium complexation reduces the overall number of synthetic steps required and thus increases the efficiency and overall yield of the reaction sequence.     

Density functional theory study of the mechanism of the acid-catalyzed decarboxylation of pyrrole-2-carboxylic acid and mesitoic acid

The mechanisms of the acid-catalyzed decarboxylation of pyrrole-2-carboxylic acid and mesitoic acid have been investigated based on density functional theory calculations at the B3LYP/6-311G (d,p) level. A polarizable continuum model (PCM) has been established in order to evaluate the effects of solvents on these reactions. The results of the calculations indicate that the first step of the acid-catalyzed decarboxylation of the pyrrole-2-carboxylic acid has two possible pathways,that is,the proton of H3O+ a...     

Deintercalation of a chemically switchable polymer from a layered silicate nanocomposite

The phenomenon of intercalation is widely known as a key process in the area of polymer/layered silicate nanocomposites. In the formation of such nanocomposites, a polymer chain is intercalated between the layers of a layered (silicate) host, typically giving a well-ordered multilayered stack with a repeat distance of only a few nanometers. Intercalated systems are excellent models for studies of confined geometries, and they often display enhanced material properties as well. In this study, we examined a series of polymers in which it was possible to reverse the intercalation process (i.e., to achieve deintercalation). Homopolymers and copolymers of poly(methyl methacrylate) and poly(tetrahydropyranyl methacrylate) (PTHPMA) were intercalated into an organically modified synthetic fluoromica. Thermally induced deprotection of the tetrahydropyranyl group resulted in the transformation of PTHPMA into poly(methacrylic acid), which was then observed to deintercalate from the silicate host. X-ray diffraction and thermogravimetric analysis were used to study the deintercalation process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3151–3159, 2003     

Asymmetric synthesis of (–)-leiocarpin A via (–)-(S)-goniothalamin employing Julia–Kocienski olefination

A concise and enantioselective syntheses of antileukemic natural products such as (–)-(S)-goniothalamin and (–)-leiocarpin A has been accomplished in excellent yields. By employing reported conditions on suitable substrates via Julia–Kocienski olefination, intramolecular lactonization, and subsequently dehydroxylative olefination, (–)-(S)-goniothalamin was synthesized. Then Sharpless asymmetric dihydroxylation–intramolecular Michael addition on (–)-(S)-goniothalamin provided (–)-leiocarpin A.     

Selective deprotection of trityl group on carbohydrate by microflow reaction inhibiting migration of acetyl group

The trityl group is an important and useful protecting group for primary hydroxy groups on carbohydrates. However, during deprotection, neighboring acetyl groups can easily migrate to the deprotected hydroxy groups. Hence, deprotection of trityl groups was optimized using a microreactor with regard to flow rate, reagent concentration, reaction time, and substrate concentration. The optimized microflow reaction conditions inhibited migration and could be applied to large-scale reactions and other substrates.     

Lewis acid-catalyzed reactions of mono-aryl group substituted methylenecyclopropanes with diethyl ketomalonate

Mono-aryl group substituted methylenecyclopropanes (MCPs) 1 react with diethyl ketomalonate 2a, an activated ketone, to give the corresponding 7-hydroxy-5-oxa-spiro[2,4]heptan-6-one derivatives 6 with syn-configuration in moderate yields in the presence of water under the catalysis of Lewis acids such as Sc(OTf)₃, Yb(OTf)₃ or In(OTf)₃ at room temperature. The reaction mechanism has been discussed on the basis of an ¹⁸O-labeling experiment.