Synthesis of a chiral phosphonium salt for the preparation of α-substituted alaninol derivatives

We herein report the synthesis of a chiral phosphonium salt, {[(4S)-4-methyl-2-oxo-1,3-oxazolidin-4-yl]methyl}(triphenyl)phosphonium iodide 13 to provide a new Wittig reagent for the general method of synthesizing α-substituted alaninol derivatives. Our method described here is widely applicable to reactions with various types of aldehyde to afford olefin products with high E-selectivity, enabling us to provide a new approach to the synthesis of chiral S1P₁ agonists including our key intermediates, and of the trace amine-associated receptor 1 (TAAR1) agonist.     

Secondary sonochemical effect on Mo-catalyzed bromination of aromatic compounds

The Molybdate-catalyzed bromination of various aromatic compounds in the presence of KBr/H(2)O(2) in an aqueous/chloroform biphasic system occurred under ultrasonic irradiation, whereas the reaction did not take place under conventional mechanical stirring (1400 rpm). The sonochemical activation was found to be of secondary effect, attributed to lowering pH by sonolysis of CHCl(3)-H(2)O solvents mixture.     

Spurring radical reactions of organic halides with tin hydride and TTMSS using microreactors

Tributyltin hydride-mediated radical reactions of organic halides were successfully carried out in a continuous flow system using a microreactor. The reactions proceeded within a very short period of time, coupled with quickly decomposing radical initiators such as V-65 and V-70. The continuous flow reaction system was applied to gram scale synthesis of a key intermediate for furofuran lignans.     

Tin-free Giese reaction and the related radical carbonylation using alkyl iodides and cyanoborohydrides

Tin-free Giese reaction and the related radical carbonylation process proceeded efficiently in the presence of sodium cyanoborohydride and tetrabutylammonium cyanoborohydride. The reaction took place chemoselectively at the carbon-iodine bond but not at the carbon-bromine and carbon-chlorine bonds. The iodine atom transfer followed by hydride reduction of the resulting carbon-iodine bond is proposed as a possible mechanism.     

Large positive magnetoresistance of insulating organic crystals in the non-ohmic region

We report a large positive magnetoresistance ratio in insulating organic crystals theta-(ET)(2)CsZn(SCN)(4) at low temperatures at which they exhibit highly nonlinear current-voltage characteristics. Despite the nonlinearity, the magnetoresistance ratio is independent of the applied voltage. The magnetoresistance ratio depends little on the magnetic field direction and is described by a simple universal function of mu(B)B/k(B)T, where mu(B) is the Bohr magneton. The positive magnetoresistance may be caused by magnetic-field-induced parallel alignment of spins of mobile and localized electrons, and a resulting blockade of electrical conduction due to the Pauli exclusion principle.     

Regioselective radical bromoallylation of allenes leading to 2-bromo-substituted 1,5-dienes

The regioselective radical bromoallylation of allenes proceeded efficiently in the presence of AIBN as a radical initiator to give 2-bromo-substituted 1,5-dienes in excellent yields. The addition of a bromine radical took place regioselectively onto the central carbon of allenes generating a stable allyl radical, which underwent addition/β-fragmentation reactions with allylbromides. The products could be further functionalized by Pd-catalyzed coupling reactions.     

Rh‐Catalyzed [5+1] and [4+1] Cycloaddition Reactions of 1,4‐Enyne Esters with CO: A Shortcut to Functionalized Resorcinols and Cyclopentenones

We have developed novel Rh‐catalyzed [n+1]‐type cycloadditions of 1,4‐enyne esters, which involve an acyloxy migration as a key step. The efficient preparation of functionalized resorcinols, including biaryl derivatives, from readily available 1,4‐enyne esters and CO was achieved by Rh‐catalyzed [5+1] cycloaddition accompanied by 1,2‐acyloxy migration. When enyne esters had an internal alkyne moiety, the reaction proceeded by a [4+1]‐type cycloaddition involving 1,3‐acyloxy migration, leading to cyclopentenones.     

Preferential extraction of left- or right-handed single-walled carbon nanotubes by use of chiral diporphyrin nanotweezers

Handedness- and diameter-based separation of single-walled carbon nanotubes was achieved through preferential extraction of 76-CoMoCAT with 2,6-pyridylene-bridged chiral diporphyrin nanotweezers.