A concise synthesis of denbinobin

A concise synthesis of denbinobin is described via an intramolecular free radical cyclization and Fremy’s salt mediated oxidation as a key reactions. A seven-step process starting from commercially available 3,5-dimethoxybenzyl bromide (6) and 2-bromoisovanillin (5) effectively constructs the natural product denbinobin (1).     

A direct synthesis of O-methyl claussequinone

The reaction of a chromene with BH(3) followed by treatment with benzoquinone and air is the key step in a direct entry to O-methyl claussequinone.     

A direct synthesis of neocryptolepine and isocryptolepine

A formal synthesis of indolequinoline alkaloid neocryptolepine and isocryptolepine is described which employed a common intermediate and used an intramolecular Wittig reaction followed by regioselective methylation in excellent yield.     

A new catalyst for direct synthesis of dimethyl ether from synthesis gas

A new catalyst has been prepared by coprecipitation sedimentation method developed in our laboratory. It exhibits excellent catalytic activity, selectivity and stability for conversion of synthesis gas to dimethyl ether: conversion of CO 92%, selectivity of dimethyl ether 98%. Catalytic properties of the catalyst show no evident change after being used for 100 h.     

A novel direct synthesis of polyol from soybean oil

As the oil crisis and environment concerning deepen,the uses of renewable resources have attracted considerable attention.Polyol intended for synthesis of polyurethane polymers was prepared by a novel direct hydroxylation of soybean oil,alternative to petroleumbased process.The transformation can afford soybean oil polyol in excellent yield with a hydroxyl number up to 467.7 mg KOH/g in the presence of OsO 4 as catalyst and NMO as oxidant.The major advantages of this approach are:two hydroxyl groups can be readily added to one double bond,replacing conventional two-step methods by an epoxidation step and then a ring opening step;a wide range of hydroxyl numbers can be obtained via varying catalyst loadings;the reaction can be performed at room temperature.The chemical structure of the polyol prepared was further characterized by chemical methods(hydroxyl number and iodine number) and spectra(1 H NMR and FTIR spectroscopy),which confirmed the cleavage of the double bonds and the produce of hydroxyl groups.     

A direct efficient diastereoselective synthesis of enantiopure 3-substituted-isobenzofuranones

Condensation of (−)-8-benzylaminomenthol with o-phthaldehyde lead to the chiral perhydro-1,3-benzoxazine 2 as single diastereoisomer. That compound reacted with different organometallics leading to 3 in excellent de. Hydrolysis of carbinols, followed by oxidation of the intermediates allowed for the synthesis of enantiopure phthalides.     

A direct synthesis of indolocarbazoles via new dinitroterphenyl precursors

The two indolocarbazoles 2 and 4 were synthesized via the reductive ring closure of dinitrodiphenylbenzenes with triethylphosphite as reducing agent in a high boiling solvent. The electrochemical behaviour of the title systems is discussed.     

A direct,stereoselective synthesis of optically active conhydrines

2-Pyridylethylcarbinol (I) has been resolved and the antipodes hydrogenated as free bases. The (+) form gave (+) conhydrine (II) while the (-) form afforded the levorotatory base stereoselectively with minor contamination of the other epimer. Hydrogenation of racemic I as well as of 2-pyridyl ethyl ketone in acid solution led formerly to the mixture of both racemates.     

A direct synthesis of 1,3-bis(bromomagnesio)propane

Careful addition of 1,3-dibromopropane

to magnesium in Et₂O yields 1,3-bis(bromomagnesio)propane

which is purified via “magnesacyclobutane”

. Reactions of

with H₂O, CO₂, HgBr₂ and Me₃SnCl are reported. MgBr₂ catalyses the decomposition of

to allylmagnesium bromide

.     

A novel three-step synthesis of Celecoxib via palladium-catalyzed direct arylation

A novel three linear step synthesis of Celecoxib was achieved in 33% overall yield via a key regioselective direct C-H arylation reaction between a 1,3-disubstituted pyrazole and an aryl bromide.     

A palladium-catalyzed alkylation/direct arylation synthesis of nitrogen-containing heterocycles

A norbornene-mediated palladium-catalyzed sequence is described in which an alkyl-aryl bond and an aryl-heteroaryl bond are formed in one reaction vessel. The aryl-heteroaryl bond-forming step occurs via a direct arylation reaction. A number of six-, seven-, and eight-membered ring-annulated indoles, pyrroles, pyrazoles, and azaindoles were synthesized from the corresponding bromoalkyl azole and an aryl iodide.     

A direct synthesis of allenes by a traceless Petasis reaction

A one-pot synthesis of allenes by the 2-nitrobenzenesulfonylhydrazide-mediated coupling of hydroxyaldehydes or ketones with alkynyl trifluoroborate salts is reported. This mild process involves in situ formation of a sulfonylhydrazone that reacts with alkynyl trifluoroborates to generate a transient propargylic hydrazide species. Decomposition of this unstable hydrazide via an intermediate monoalkyldiazine produces the allene products through an alkene walk mechanism.     

A new synthetic strategy for the synthesis of bioactive stilbene dimers. A direct synthesis of amurensin H

2,3-Diarylbenzofurans are efficiently generated by the cyclization of ortho-benzyloxybenzophenones using the hindered phosphazene base P₄-t-Bu.     

Allocolchicinoid synthesis via direct arylation

[reaction: see text] A formal enantioselective synthesis of allocolchicine and a synthesis of a C-ring analogue have been achieved by employing an intramolecular direct arylation of an aryl chloride to form the biaryl carbon-carbon bond and the seven-membered ring.