Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis

A series of ferrocene-fused planar-chiral N-tosyl-4-pyridones (S)-2b-d were prepared in enantiomerically pure forms. Starting with the chiral ferrocenyl acetals, 1-[(2S,4S)-4-methoxymethyl-1,3-dioxan-2-yl]-1',2',3',4',5'-R5-ferrocenes ((–)-3b, R = Me; (–)-3c, R = Ph; (–)-3d, R = Bn), N-tosylamino and formyl groups were introduced at the 1- and 2-positions of the ferrocene cores in (S)-11b-d with control of the planar chirality. After the reaction with ethynylmagnesium bromide, generated propargyl alcohol derivatives (S)-17 were treated with MnO2 and catalytic TBAI to give the planar-chiral pyridones by the iodide-catalyzed cyclization. This method is highly practical with a shorter and higher-yield sequence without using noble metal catalysts. Planar-chiral ferroco-pyridones (S)-2b-d were reacted with various Me3Si-NR'2 to give a library of ferrocene-fused 4-dialkylaminopyridines ((S)-1, DAAPs) in high yields as single-enantiomers by the detosylative amination. The cymantrene-fused DAAPs were also prepared in the same way. The library of the chiral DAAPs were examined in the two asymmetric reactions as organocatalysts, and some newly prepared Fc-DAAPs showed better enantioselectivity than the known species

ALMA 0.02"-resolution observations reveal HCN-abundance-enhanced counter-rotating and outflowing dense molecular gas at the NGC 1068 nucleus

We present ALMA ~0.02"-resolution observations of the nucleus of the nearby (~14 Mpc) type-2 AGN NGC 1068 at HCN/HCO+/HNC J=3-2 lines, as well as at their 13C isotopologue and vibrationally excited lines, to scrutinize the morphological/dynamical/chemical/physical properties of dense molecular gas in the putative dusty molecular torus around a mass-accreting supermassive black hole. We confirm almost east-west-oriented dense molecular gas emission both morphologically and dynamically, which we regard as coming from the torus. Bright emission is compact (<3 pc), and low-surface-brightness emission extends out to 5-7 pc. These dense molecular gas properties are not symmetric between the eastern and western torus. The HCN J=3-2 emission is stronger than the HCO+ J=3-2 emission within the ~7 pc torus region, with an estimated dense molecular mass of (0.4-1.0)x10^6Msun. We interpret that HCN abundance is enhanced in the torus. We detect signatures of outflowing dense molecular gas and a vibrationally excited HCN J=3-2 line. Finally, we find that in the innermost (<1 pc) part of the torus, the dense molecular line rotation velocity, relative to the systemic velocity, is the opposite of that in the outer (>2 pc) part, in both the eastern and western torus. We prefer a scenario of counter-rotating dense molecular gas with innermost almost-Keplerian-rotation and outer slowly rotating (far below Keplerian) components. Our high-spatial-resolution dense molecular line data reveal that torus properties of NGC 1068 are much more complicated than the simple axi-symmetrically rotating torus picture in the classical AGN unification paradigm.Comment: 45 pages, 20 Figures. Accepted for publication in Ap

Effect of the Rotational Speed of a Long Jump Rope in a Person Turning the Rope on Heart Rate and Oxygen Uptake

The purpose of this study was to clarify the effect of different rotational speeds on the heart rate (HR) and oxygen uptake of a person turning a long jump rope. The subjects consisted of six healthy Japanese males who volunteered to participate in the study. They were asked to turn a long jump rope. The measurement was set at three rotational speed conditions: 70, 90 and 110 rpm. The measurement indexes were HR, oxygen uptake, rating of perceived exertion and blood pressure. The 90 and 110 rpm conditions demonstrated significant HR increases from the first to the third minute of the 3-minute exercise compared with the 70 rpm condition. The 110 rpm condition showed significant HR increases from the first to the third minute compared with the 90 rpm condition. The 90 and 110 rpm conditions demonstrated significant oxygen uptake increases from the first to the third minute compared with the 70 rpm condition. The 110 rpm condition showed significant oxygen uptake increases from the first to the third minute compared with the 90 rpm condition. The changes in the HR and oxygen uptake of the rope turner were dependent on the rotational speed of the long jump rope