Because of the high reactivity of Grignard reagents a direct highly enantioselective Grignard reaction with aldehydes has lately been disclosed In this report. Grignard leagents were: introduced with bis[2-(N,N'-dimethylamino)ethyl) ether (BDMAEF) to effectively deactivate then reactivity thus a highly enantioselective alkylation of aldehydes with Grignard reagents resulted from catalysis by (S)-BINOL-Ti(O'Pt)(2). It is thought that BDMAEE chelates the in situ generated salts MgBt(2) from Schlenk equilibrium of RMgBr and Mg(O'Pt)Br from transmetalation of RMgBt with Ti(O'Pt). The Mg salt can actively promote the undesired background reaction to give the racemate I he chelation definitely inhibits the catalytic activity of the Mg salts suppresses the unwanted background reaction, and enables the highly enantioselective addition catalyzed by (S)-BINOL-Ti(O'Pt)(2) Consequently, the Mg salt byproducts were not removed. less Ti(O'Pt)(4) than RMgBr was used. and extremely low temperature was avoided in this catalytic asymmetric reaction in comparison with the research disclosed before Various alkyl Grignard leagents were investigated in the asymmetric addition and 'BuMgBr resulted in the highest enantioselectivity. >99% Furthermore important intermediate secondary arylpropanols for chiral drug synthesis were effectively synthesized with high enantioselectivity, up to 97%, in one step
Isoprene-derived epoxydiols (IEPOX) are identified in ambient aerosol samples for the first time, together with other previously identified isoprene tracers (i.e., 2-methyltetrols, 2-methylglyceric acid, C(5)-alkenetriols, and organosulfate derivatives of 2-methyltetrols). Fine ambient aerosol collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS) was analyzed using both gas chromatography/quadrupole mass spectrometry (GC/MS) and gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) with prior trimethylsilylation. Mass concentrations of IEPOX ranged from approximately 1 to 24 ng m(-3) in the aerosol collected from the two sites. Detection of particle-phase IEPOX in the AMIGAS samples supports recent laboratory results that gas-phase IEPOX produced from the photooxidation of isoprene under low-NO(x) conditions is a key precursor of ambient isoprene secondary organic aerosol (SOA) formation. On average, the sum of the mass concentrations of IEPOX and the measured isoprene SOA tracers accounted for about 3% of the organic carbon, demonstrating the significance of isoprene oxidation to the formation of ambient aerosol in this region.