InCl3/Al mediated pinacol coupling reactions of aldehydes and ketones in aqueous media

A systematic work on the homo-pinacol coupling reactions of benzophenones, aldehydes, and acetophenones in aqueous media with InCl₃/Al is described for the first time, in which various 1,2-diols are obtained in moderate to good yields.     

Room temperature-stable electride as a synthetic organic reagent: application to pinacol coupling reaction in aqueous media

Room temperature-stable inorganic electride [Ca(24)Al(28)O(68)](4+)4e(-) was employed for a pinacol coupling reaction in aqueous media. Ca-Al-O gel formed by the destruction of the crystal structure of an electride by water media played a key role in transferring the electron to electrophilic aldehydes. Aromatic aldehydes reacted smoothly with moderate to high yields.     

Samarium mediated pinacol coupling of carbonyl compounds in the presence of a catalytic amount of iodine under aqueous media

In the presence of a catalytic amount of iodine, metallic samarium mediated pinacol coupling of carbonyl compounds has been carried out under saturated aqueous NH4Cl-THF conditions at room temperature. It gives corresponding 1,2-diols in good yields.     

Concise total synthesis of the aporphine alkaloid 7,7''-bisdehydro-O-methylisopiline by an InCl3 mediated cycloisomerization reaction

A novel InCl3 mediated cycloisomerization reaction leading to 10-halophenanthrene derivatives constitutes the key step of the first total syntheses of O-methyldehydroisopiline 10 and 7,7'-bisdehydro-O-methylisopiline 11, two prototype members of the aporphine family of alkaloids.     

Samarium diiodide-induced intramolecular pinacol coupling of dinitrones: synthesis of cyclic cis-vicinal diamines

Pinacol coupling of alkyl dinitrones mediated by SmI2 was achieved in the presence of a proton source allowing the synthesis of cyclic vicinal diamines with good cis-selectivity.     

Vanadium-catalyzed pinacol coupling reaction in water

A catalytic pinacol coupling using water as a solvent was performed by a catalytic amount of vanadium(III) chloride and metallic Al as a co-reductant. A combination forms a binary catalytic system, being in sharp contrast to the reaction in organic solvent, which requires a chlorosilane as an additive. Various aromatic aldehydes underwent the reductive coupling to give the corresponding 1,2-diols in moderate to good yields.     

Reexamination of CeCl3 and InCl3 as activators in the diastereoselective Mukaiyama aldol reaction in aqueous media

A search for suitable reaction conditions in Mukaiyama-type aldol condensations activated by CeCl(3) and InCl(3) revealed that the reaction proceeds best in i-PrOH/H(2)O (95:5). Contrary to literature precedent, no reaction was observed in pure water, and the encountered destruction of the starting silyl enol ether can be ascribed to initial hydrolysis of the Lewis acid. As anticipated from the dual parameter (pK(h), WERC value) characteristics of CeCl(3) and InCl(3), the former proved more efficient as Lewis acid-promoter, in terms of reaction speed and yield. Nevertheless, InCl(3) was a superior catalyst during evaluation of the diastereoselectivity of the process. In this regard, determination of diastereoselectivity as a function of time showed that the InCl(3)-catalyzed reaction is irreversible, whereas the CeCl(3)-catalyzed reaction is a reversible process. In both cases, formation of the syn product is kinetically preferred, although DeltaDeltaG(++)273K(InCl(3)) = 1.50 kcal/mol versus DeltaDeltaG(++)273K (CeCl(3)) = 0.38 kcal/mol. Molecular modeling (semiempirical PM3, ab initio HF/3-21G*, hybrid B3LYP/3-21G*, and B3LYP/LANL2DZ) of the diastereoselective aldol reaction promoted by InCl(3) supports a "closed", Zimmermann-Traxler transition state.     

Diastereoselective inter- and intramolecular pinacol coupling of aldehydes promoted by monomeric titanocene(II) complex Cp(2)TiPh

A monomeric titanocene(III) derivative, Cp(2)TiPh, effectively promoted the pinacol coupling of both an aromatic aldehyde, benzaldehyde, and an aliphatic aldehyde, 3-phenylpropionaldehyde. The same reactive complex was successfully generated by a catalytic amount of a precursor, Cp(2)Ti(Ph)Cl, and its stoichiometric amount of Zn. The Cp(2)TiPh-catalyzed pinacol coupling of benzaldehyde derivatives and aliphatic aldehydes afforded the corresponding 1,2-diols in high yields with moderate to good threo-selectivity. On the other hand, Cp(2)TiPh-catalyzed pinacol cyclization of dials gave cyclic 1,2-diols with excellent diastereoselectivity. The extension of this protocol to chiral dials demonstrated that the phenyltitanium complex catalytically transmitted an axial chirality or a central chirality of the starting dials to the central chirality of the resultant 1,2-diols.     

Reduction and coupling reaction of carbonyl compounds by KI/Fe(OH)3 in aqueous media

ABSTRACT

A small amount of ferric hydroxide was found to catalyze KI-activated coupling of aromatic aldehydes and acetophenone to give the corresponding pinacols in high yields. The ratio of meso to dl isomer was approximately 1:1. Most aliphatic aldehydes and ketones were unreactive under the same conditions.     

Diastereoselective and enantioselective photoredox pinacol coupling promoted by titanium complexes with a red-absorbing organic dye

The pinacol coupling reaction, a reductive coupling of carbonyl compounds that proceeds through the formation of ketyl radicals in the presence of an electron donor, affords the corresponding 1,2-diols in one single step. The photoredox version of this transformation has been accomplished using different organic dyes or photoactive metal complexes in the presence of sacrificial donors such as tertiary amines or Hantzsch''s ester. Normally, the homo-coupling of such reactive ketyl radicals is neither diastereo- nor enantio-selective. Herein, we report a highly diastereoselective pinacol coupling reaction of aromatic aldehydes promoted by 5 mol% of the non-toxic, inexpensive and available Cp₂TiCl₂ complex. The key feature that allows the complete control of diastereoselectivity is the employment of a red-absorbing organic dye in the presence of a redox-active titanium complex. Taking advantage of the well-tailored photoredox potential of this organic dye, the selective reduction of Ti(iv) to Ti(iii) is achieved. These conditions enable the formation of the d,l (syn) diastereoisomer as the favored product of the pinacol coupling (d.r. > 20 : 1 in most of the cases). Moreover, employing a simply prepared chiral SalenTi complex, the new photoredox reaction gave a complete diastereoselection for the d,l diastereoisomer, and high enantiocontrol (up to 92% of enantiomeric excess).

A metallaphotoredox, diastereoselective and enantioselective pinacol coupling reaction promoted by titanium complexes with the use of a red-absorbing organic dye was developed.     

Efficient synthesis of functionalized butenolides mediated by vinyltriphenylphosphonium salts in aqueous media

An efficient synthesis of 5-oxo-2,5-dihydro-3-furancarboxylate derivatives via reaction of dialkyl acetylenedicarboxylate with triphenylphosphine（Ph₃P） in the presence of activated carbonyl compounds such as ethyl pyruvate,benzil,benzoylcyanide, biacetyle or N-alkylisatins is described.     

Enantioselective pinacol coupling reaction of aromatic aldehydes catalyzed by chiral vanadium complexes

The asymmetric pinacol coupling of aromatic aldehydes by chiral salan–vanadium complexes as effective catalysts is reported. Chiral 1,2-diols were obtained with high diastereoselectivities (up to 90/10) and moderate to high enantioselectivities (up to 82% ee). The possible mechanism of the pinacol coupling reaction is also discussed.     

Effect of fluoride salts on metal-mediated reactions. Aluminum/fluoride salt-mediated reduction and pinacol coupling of carbonyl compounds in aqueous media

[formula: see text] Metal fluoride salts were found to activate aluminum in water to react with carbonyl compounds to give the pinacol coupling products and/or the reduced alchohols. The metal ion of the fluoride salt was found to play a role in controlling the chemoselectivity and stereoselectivity of the reaction.     

In/InCl(3)-Mediated cross-coupling reactions of methyl vinyl ketone with benzaldehyde in aqueous media

Various beta,gamma-unsaturated ketones were successfully prepared by cross-coupling reactions of methyl vinyl ketone (MVK) with benzaldehydes mediated by In/InCl(3) in aqueous media.     

DBSA mediated chemoselective synthesis of 2-substituted benzimidazoles in aqueous media

An efficient synthetic method has been developed for the facile synthesis of 2-substituted benzimidazoles in organized aqueous media in the presence of a surfactant (viz. DBSA) as catalyst and I₂ as co-catalyst. The method described has the advantages of operational simplicity, excellent yields, high chemoselectivity, and clean and green reaction profile.     

McMurry coupling of aryl aldehydes and imino pinacol coupling mediated by Ti(O-i-Pr)4/Me3SiCl/Mg reagent

Ti(O-i-Pr)₄/Me₃SiCl/Mg reagent mediated McMurry coupling of aryl aldehydes to biaryl olefins at near room temperature. This low valent titanium (LVT) reagent also mediated the coupling of aldimines to 1,2-diamines (imino pinacol coupling).     

Synthesis of planar-chiral paracyclophanes via samarium(II)-catalyzed intramolecular pinacol coupling

[reaction: see text] A series of [n]paracyclophanediols (n = 8-12) was synthesized by samarium-catalyzed pinacol coupling for their ansa-bridge formation. Enantiomerically pure [n]paracyclophane esters were derived from the diols in a several steps via chiral resolution (for n = 10) or via crystallization-induced asymmetric transformation (for n = 11) by using amino alcohol auxiliaries and their selective cleavages.     

Research on Liebeskind-Srogl coupling/intramolecular Diels-Alder reaction cascade

The Liebeskind-Srogl coupling/intramolecular Diels-Alder (IMDA) reaction cascade that stereoselectively affords a tricarbocyclic compound with a trans–trans-cis fused ring system including an all-carbon quaternary stereogenic center at the ring junction is described. The cascade reactions proceed quickly and stereoselectively afford the products within 2?h at room temperature in the presence of a suitable thioester. The developed protocol as well as the prepared chiral compounds are useful for the enantioselective total synthesis of terpenoids with the trans–trans-cis fused ring system.     

Palladium-catalyzed coupling reaction of propargylic oxiranes with arylboronic acids in aqueous media

A novel type of coupling reaction has been developed by the palladium-catalyzed reaction of propargylic oxiranes with arylboronic acids, in which anti-substituted 4-aryl-2,3-allenols were produced in a highly diastereoselective manner. A chiral-substituted allene has been synthesized from the reaction of a chiral propargylic oxirane without loss of the chirality.