New synthesis of ortho esters of sugars

Summary A new synthesis of ortho esters of sugars has been proposed, starting with 1,2-cis-halogenoses in ethyl acetate medium.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12 p. 2214–2216, December, 1964     

Xyloccensins O and P, unique 8,9,30-phragmalin ortho esters from Xylocarpus granatum

Two unique 8,9,30-phragmalin ortho esters, xyloccensins O (1) and P (2), were isolated from the mangrove plant Xylocarpus granatum. They are a new type of ortho ester of phragmalin. The structures were determined by spectroscopic and single-crystal X-ray diffraction techniques. The biogenetic pathway to these new phragmalins was also proposed. [structure: see text]     

Stereoselective and regioselective reaction of cyclic ortho esters with phenols

Cyclic ortho esters undergo stereoselective and regioselective reaction with phenols when treated with BF(3) x OEt(2) at low temperatures. Attack of the phenol on the ortho ester occurs at an open carbon para to electron-donating groups on the phenol ("C-addition") or at the phenolic hydroxyl group ("O-addition") depending on the nature of the cation formed from reaction of the ortho ester and BF(3) x OEt(2). Products resulting from O-addition undergo reversion to a mixture of starting phenol, C-addition product, and O-addition product if treated with BF(3) x OEt(2) at room temperature, but C-addition products are stable under the same conditions. X-ray structural analysis of the C-addition compound indicates that its stereochemistry is opposite to that observed in reaction of similar ortho esters with chloride from TMSCl. However, the stereochemistry of the reaction can be rationalized by the ability of the ortho ester to isomerize via an intermediate benzylic cation and examination of the preferred trajectory of attack of the nucleophile on the intermediate oxonium ion.     

Behavior of aromatic ortho esters under chemical ionization conditions

Conclusions Ortho esters decompose under protolysis conditions in the gas phase to form carboxonium ions [MH-RHO]⁺, which can give stable associates with neutral molecules.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 579–583, March, 1988.     

Synthesis and characterization of new ointment-like poly(ortho esters)

Ointment-like poly(ortho esters) were synthesized for the first time from the reaction of 3,9-bis(methylene)-2,4,8,10-tetraoxaspiro[5. 5] undecane with poly(ethylene glycol)-400, N,N-bis(2-hydroxyethyl)-n-hexadecylamine and N,N-bis(2-hydroxyethyl) palmitamide, respectively. The obtained polymers were characterized by 1H NMR spectra, 13C NMR spectra, elemental analyses, light scattering, and measurements of intrinsic viscosity. The influence of catalyst on the intrinsic viscosity of polymers was investigated. The 9-[(1,3-dihydroxy-2-propoxy) methyl] guanine controlled release profiles of hydrophobic ointment-like polymers such as polymer P_II in vitro were also discussed.     

Copolymerization of unsaturated spiro ortho esters with maleic acid derivatives

The formation of charge-transfer (CT) complexes of unsaturated spiro ortho esters such as 2-methylene-1,4,6-trioxaspiro[4.4]nonane(I) and 2-methylene-1,4,6-trioxaspiro[4.6]undecane(II) with maleic acid derivatives such as maleic anhydride (Manh), dimethyl maleate (DMM), and N-ethyl maleimide (NEM) was ascertained by ultraviolet (UV) and nuclear magnetic resonance (NMR) spectroscopy. The stoichiometries of these complexes were estimated as 1:1. The determination of their equilibrium constants (K) was attempted by using the Hanna-Ashbough equation with NMR spectroscopy. Although K values for I-DMM and II-DMM were specified as 0.266 and 0.336 L/mol, respectively, those for the other systems could not be obtained but were assumed to be negligible small (K ? 1). Copolymerization of these systems which was carried out without an initiator determined that spontaneous copolymerization occurs in all cases but that the copolymerization rates of I-DMM and II-DMM systems are slow. The systems in which Manh or DMM was used as an acceptor monomer gave the alternating copolymers at various monomer to feed ratios. The terpolymerizaton of the I–Manh–DMM system established that DMM takes little part in giving the alternating copolymers I and Manh. Consequently, it was assumed that the reactivity of the CT complex monomer is dependent on the contribution of the dative structure to CT complex.     

Synthesis of Polysubstituted Iodoarenes Enabled by Iterative Iodine‐Directed para and ortho C−H Functionalization

Among halogenated aromatics, iodoarenes are unique in their ability to produce the bench‐stable halogen(III) form. Earlier, such iodine(III) centers were shown to enable C?H functionalization ortho to iodine via halogen‐centered rearrangement. The broader implications of this phenomenon are explored by testing the extent of an unusual iodane‐directed para C?H benzylation, as well as by developing an efficient C?H coupling with sulfonyl‐substituted allylic silanes. Through the combination of the one‐shot nature of the coupling event and the iodine retention, multisubstituted arenes can be prepared by sequentially engaging up to three aromatic C?H sites. This type of iodine‐based iterative synthesis will serve as a tool for the formation of value‐added aromatic cores.     

Cationic ring-opening transfer polymerization of spiro ortho esters initiated by carbon black

The ring-opening transfer polymerization of spiro ortho esters (SOE) initiated by carbon black was investigated. In the absence of carbon black, no polymerization occurred at all. In the presence of channel black containing carboxyl group, the ring-opening transfer polymerization of SOE was initiated at 50-70°C. to give polyether ester, namely alternating copolymer of epoxide and lactone. The rate of polymerization of 1,4,6-trioxaspiro[4.4]nonane and 1,4,6-trioxaspiro[4.5]decane was considerably small compared with that of 1,4,6-trioxaspiro[4.6]undecane. The activation energy of the polymerization of 2-chloromethyl-1,4,6-trioxaspiro[4.6]undecane was estimated to be 6.0 kcal/mol. The initiating activity of carbon black increased with an increase in carboxyl group content of carbon black. Furnace black that contained no carboxyl group was unable to initiate the polymerization. Furthermore, the carbon black lost the initiating ability of the polymerization upon the blocking of carboxyl group on the surface by the treatment with potassium hydroxide or diazomethane. Based on these results, it was concluded that carboxyl group on carbon black plays an important role in the initiation. During the polymerization, a part of the polymer formed was grafted onto carbon black: the grafting ratio was 10–30%. The mechanisms of initiation and grafting were discussed.     

Synthesis of Polysubstituted Pyrrolizidines from Proline Derivatives and Conjugated Nitroolefins

The stereochemistry of 1,3-dipolar cycloaddition of azomethine ylides derived from aromatic aldehydes and i-proline alkyl esters with several nitroolefins was investigated. Cyclic and acyclic nitroolefins add to the anti form of the ylide in a highly diastereoselective but poorly regioselective manner to give pyrrolizidine derivatives. In a few cases, the stereochemical results strongly support a stepwise mechanism.     

Synthesis of ortho substituted arylboronic esters by in situ trapping of unstable lithio intermediates

[reaction: see text] Ortho lithiation-in situ boration using lithium 2,2,6,6-tetramethylpiperidide (LTMP) in combination with triisopropylborate (B(OiPr)(3)) is a highly efficient and experimentally straightforward process for the preparation of ortho substituted arylboronic esters. The mild reaction conditions allow the presence of functionalities such as ester or cyano groups or halogen substituents that are usually not compatible with the conditions used in directed ortho metalation of arenes. The arylboronic esters underwent Suzuki-type cross-coupling with a range of aryl halides, furnishing biaryls in 53-94% yield.     

Reactions of indoles with ortho esters,N,N-dimethylformamide and N,N-dimethylacetamide dialkyl acetals

Indole and N-methylindole react with oxa stabilized carbocations generated in situ from orthoformates to yield tris(3-indolyl)methane. The unsymmetrical isomers, e.g. 2-(N-methyl-3-indolyl)di(N-methyl-3-indolyl)-methane ( 4 ), were not formed as established by an independent synthesis. N,N-Dimethylacetamide dimethyl-acetal reacted with 2-alkyl substituted indoles to produce 1,1-bis(3-indolyl)ethanes ( 3 ).     

Two phthalide dimers from the radix of Angelica sinensis

The phytochemical investigation of extracts from the radix of Angelica sinensis yielded a new phthalide dimer, 3,3'Z-6.7',7.6'-diligustilide, along with a known dimer, levistolide A. Their structures were established on the basis of spectral data, particularly using 1D-NMR and several 2D shift-correlated NMR pulse sequences (1H-1H COSY, HSQC, HMBC and NOESY).