Sonogashira cross-coupling of 3-bromo-1,2-diones: an access to 3-alkynyl-1,2-diones

A new general method for the synthesis of enols of cyclic 3-alkynyl-substituted 1,2-diketones is developed. Sonogashira cross-coupling of silyl enolates of cyclic 3-bromo-cyclopentane- and 3-bromo-cyclohexane-1,2-diones with variety of substituted acetylenes afforded enols of cyclic 3-alkynyl-1,2-diones with good yields (up to 93%) in a short reaction time. The starting 3-bromo-1,2-diones are easily obtainable by direct bromination of 1,2-diones with NBS.     

Regioselective synthesis of C-2 substituted imidazo[4,5-b]pyridines utilizing palladium catalysed C–N bond forming reactions with enolizable heterocycles

In this Letter we report a rapid and facile access to C2-substituted imidazo[4,5-b]pyridine analogues utilizing palladium mediated Buchwald–Hartwig cross-coupling reactions. The use of enolizable heterocycles as cross-coupling partners resulted in a wide range of imidazo[4,5-b]pyridine analogues which are prone to have medicinal relevance. Xantphos and Pd(OAc)₂ were found to be more effective for the coupling of 2-halo imidazo[4,5-b]pyridines with pyridone nucleophiles. A regioselective approach for the synthesis of 2-substituted 3H-imidazo[4,5-b]pyridine and 1H-imidazo[4,5-b]pyridine is also reported.     

An appraisal of the Suzuki cross-coupling reaction for the synthesis of novel fluorescent coumarin derivatives

We report the chemical design and development of 3-aryl-substituted 7-alkoxy-4-methylcoumarins with enhanced fluorogenic properties. The 3-aryl substituents are installed via an optimized Suzuki–Miyaura cross-coupling (SMC) reaction between a 7-alkoxy-3-bromo-4-methylcoumarin and aryl boronic MIDA esters using Pd(OAc)₂/XPhos in a catalytic system with K₂CO₃ in aqueous THF. Under these conditions, an exocyclic ester functionality is found to be unaffected. Subsequent saponification revealed a carboxylic acid functionality that is suitable for conjugation reactions. Evaluation of their fluorescence properties indicated that the installed 3-heteroaryl substituent, particularly benzofuran-2-yl, resulted in a significant red shift of both the excitation and emission wavelengths.     

Suzuki–Miyaura cross-coupling reaction of 1,2-oxaborol-2(5H)-ols with carboxylic anhydrides: a new method to furans

An efficient one-step method has been developed to construct furans via a Suzuki–Miyaura cross-coupling reaction of 1,2-oxaborol-2(5H)-ols with carboxylic anhydrides. In the presence of Pd(OAc)₂/PCy₃, the multi-substituted alkenylboron compounds could couple with anhydrides to obtain furans in moderate-to-good yields. The addition of bases promoted the coupling reaction, and the plausible reaction mechanism was proposed.     

Stereoselective total synthesis of oplopandiol,oploxyne A,and oploxyne B

A stereoselective total synthesis of oplopandiol, oploxyne A, and (−)-oploxyne B is described. The key reactions include Sharpless asymmetric epoxidation, d-proline catalyzed aminoxylation, Cadiot–Chodkiewicz cross-coupling reaction, m-CPBA induced substrate-controlled stereoselective epoxidation, and Lewis acid catalyzed stereo- and regioselective ring-opening of epoxide.     

Imidazolidinium ferrate complexes: Synthesis and catalytic properties

The new well-defined and air stable anionic iron complexes bearing an imidazolidinium ligand (2a–d) have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction studies. Starting from FeBr₂, [imidazolidinium][FeBr₄] complexes 2a and 2b were prepared. The reaction of imidazolidinium chlorides with Fe(OAc)₂, followed by a recrystallization in the air led to bis(imidazolidinium) μ-oxido-bis[trichloroferrate(III)] complexes 2c and 2d. The catalytic activity of these novel complexes has been evaluated in the cross-coupling reactions of alkyl halides with Grignard reagents.     

Design and Synthesis of New 5-aryl-4-Arylethynyl-1H-1,2,3-triazoles with Valuable Photophysical and Biological Properties

Cu-catalyzed 1,3-dipolar cycloaddition of methyl 2-azidoacetate to iodobuta-1,3-diynes and subsequent Suzuki-Miyaura cross-coupling were used to synthesize new triazoles derivatives: 5-aryl-4-arylethynyl-1H-1,2,3-triazoles. Investigation of their optical properties by using UV absorption and fluorescence emission spectroscopies revealed that all molecules possess fluorescence properties with the values of the Stokes shift more than 100 nm. The photophysical behavior of the two most promising triazoles in polar and non-polar solvents was also studied.     

Enantioselective Total Synthesis of (+)-Nordasycarpidone, (+)-Dasycarpidone,and (+)-Uleine

The structure of uleine type alkaloids is characterized by the presence of a bridged tetracyclic hexahydro-1H-1,5-methanoazocino[4,3-b]indole ring system 1 . Various strategies have been developed to access this polycyclic structural motif. We report herein a one-step conversion of appropriately functionalized 1,3,4-trisubstituted cyclopent-1-ene to 1 by way of an integrated oxidation/reduction/cyclization (iORC) process. This domino sequence, initiated by oxidative cleavage of cyclopentene ring, generated subsequently a cyclohexenone, an indole and a 1,3-bridged piperidine ring through formation of one C−C and two C−N bonds. Compound 1 is subsequently converted to nordasycarpidone, dasycarpidone and uleine. The chirality of the molecule was introduced by enzymatic desymmetrization of commercially available meso cis-3,5-diacetoxy-1-cyclopentene.     

Negishi Cross-Coupling Provides Alkylated Tryptophans and Tryptophan Regioisomers

Mild transition-metal catalysed cross-couplings enable direct functionalisation of biocatalytically halogenated tryptophans with alkyl iodides, representing a new alternative for late-stage derivatisations of halogenated aromatic amino acids. Moreover, this strategy enables preparation of (homo)tryptophan regioisomers in a simple two-step synthesis using a Pd-catalysed Negishi cross coupling. This method provides access to non-canonical constitutional surrogates of tryptophan, ready for use in peptide synthesis.     

Stereospecific 1,2-Migrations of Boronate Complexes Induced by Electrophiles

The stereospecific 1,2-migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2-migration of boronate complexes is driven by displacement of an α-leaving group, oxidation of an α-boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile-induced stereospecific 1,2-migration of groups from boron to sp² and sp³ carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2-migration of boronate complexes: stereospecific Zweifel-type reactions, catalytic conjunctive coupling reactions, and transition metal-free sp²–sp³ couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented.