Junji Inanaga

SmI2-induced reductive cross-coupling of carbonyl compounds with (α,β-unsaturated esters☆

Reductive cross-coupling of carbonyl compounds with(α,β-unsaturated esters by SmI2 to ?-lactones was highly accelerated by the addition of hexamethylphosphoric triamide (HMPA).

A highly stereoselective pinacolization of aromatic and α, β-unsaturated aldehydes.dta mediated by titanium(III)-magnesium(II) complex

Abstract Reduction of Cp 2 TiCl 2 with sec -BuMgCl in THF gave a greenish deep brown solution which has been found to promote the reductive homocoupling of aromatic and α, β-unsaturated aldehydes to yield symmetrical 1, 2-diols with high threo -selectivity.

A facile reductive dimerization of conjugated acid derivatives with samarium diiodide

Conjugated esters were instantaneously hydrodimerized at room temperature by use of the reduction system, Sml2-THF-HMPA, in the presence of proton sources. A perfect stereoselection was realized in the reaction of N,N-dibenzyl crotonamide.

Remarkable ligand effect on the enantioselectivity of the chiral lanthanum complex-catalyzed asymmetric epoxidation of enones

Abstract The addition of triphenylphosphine oxide significantly enhanced the degree of asymmetric induction (up to 96% ee) in the chiral La-BINOL-complex-catalyzed epoxidation of enones using tert -butyl hydroperoxide as the oxidant. The new protocol is highly general and practical.

SmI2-induced highly regioselective reduction of α,β-epoxy esters and γ,δ-epoxy-α,β-unsaturated esters: an efficient route to optically active β-hydroxy and δ-hydroxy esters

Abstract α,β-Epoxy esters were rapidly reduced at room temperature to yield β-hydroxy esters with retention of the configurations at the β-carbon atoms by using SmI 2 -THF-HMPA system in the presence of N,N-dimethylaminoethanol (DMAE). The conditions were successfully applied to the synthesis of vinylogous δ-hydroxy esters.

Recent progress of N-heterocyclic carbenes in heterogeneous catalysis

The aim of this tutorial review is to highlight the potential application of N-heterocyclic carbenes (NHC) in heterogeneous catalysis. The unique combination of the high reactivity of NHCs together with the ease of separation, purification and recyclability of the solid catalyst makes the heterogeneous system one of the most promising strategies for the synthesis of fine chemicals on an industrial scale. This tutorial review focuses on the most representative examples of this nascent research area and highlights recent achievements of NHCs in heterogeneous catalysis (other than metathesis reactions). We hope this serves as inspiration for further progress in this field.

Sml2-promoted aryl radical cyclization. A new synthetic entry into heterocycles

Abstract Benzofuran, naphthofuran, and indole frameworks were expediently constructed at ambient temperature from arene bromides with ortho O- and N-substituents containing double or triple bonds via radical cyclization process promoted by Sml 2 .

A highly efficient deoxygenation of α-oxygenated esters via SmI2-induced electron transfer process

Abstract A variety of α-oxygenated esters, such as α-acetoxy-, α-methoxy-, α-OTHP, and α-hydroxy esters were easily reduced at room temperature to give the corresponding saturated esters in good to excellent yields with the aid of an efficient electron transfer system, SmI2-THF-HMPA. The method was successfully applied to the direct conversion of (R,R)-tartrates to (R)-malates.

Preparation of medium- and large-ring lactones. SmI2-induced cyclization of ω-(α-bromoacyloxy) aldehydes☆

Abstract ω-Bromoacetoxy- andω-(α:-bromopropionyloxy) aldehydes were cyclized by SmI 2 giving 8- to 14-membered ringβ-hydroxy lactones in excellent yields.

Reductive coupling of allylic acetates with carbonyl compounds by using Pd(0)-SmI2 system

Abstract Reductive coupling of allylic acetates with carbonyl compounds proceeded by SmI 2 in the presence of catalytic Pd(0) to yield homoallylic alcohols.