A Highly diastereoselective synthesis of (1R)-(+)-camphor-based chiral allenes and their asymmetric hydroboration-oxidation reactions

Synthesis of camphor derived chiral allenes and their hydroboration-oxidation reactions are described. Reaction of (1R)-(+)-camphor with alkynyllithium followed by the reduction of the resulted propargyl alcohol derivatives using AlH3 furnished chiral allenes 2a-g in excellent yields with high diastereoselectivity. Reduction of the propargyl alcohols with aluminum hydride proceeded through selective intermolecular anti-addition of hydride ion. The stereochemistry of the chiral allenes 2 was assigned based on lanthanide shift studies and chemical correlations. Diastereoselectivity was observed in the hydroboration-oxidation of 2 which produced a mixture of (E,R) and (E,S) stereoisomers in a ratio of 6:1 to 18:1.     

Expedient, stereocontrolled synthesis of (+)-compactin lactone via intramolecular Reformatsky reaction

A concise, stereodefined synthesis of compactin lactone is described. Samarium(II) iodide mediated intramolecular Reformatsky reaction is the key step in the synthesis.     

Development of β-hydroxyamide/titanium complexes for catalytic enantioselective silylcyanation of aldehydes

A highly enantioselective addition of trimethylsilylcyanide to aldehydes catalyzed by chiral titanium complexes is described. The chiral titanium complexes were prepared in situ from Ti(OⁱPr)₄ and β-hydroxyamide ligands, that could easily be synthesized from ketopinic acid and C₂ symmetrical chiral diamines in a small number of steps.     

Asymmetric synthesis of functionalized diarylmethanols catalyzed by a new gamma-amino thiol

[reaction: see text] A mild asymmetric arylation of aromatic aldehydes catalyzed by gamma-amino thiol 5 gave the corresponding diarylmethanols with 95 to >99.5% ee.     

Determination of microamounts of iron by hydroxamate resin colorimetry

Summary A new, sensitive chelating ion-exchanger colorimetric method has been developed for the determination of iron at the g/l level in water, based on the direct measurement of light absorption of iron hydroxamate resin complex. In 0.2 N perchloric acid solution, iron could be rapidly, selectively and quantitatively absorbed on the hydroxamate resin. The calibration curve for iron(III) of a 25 ml solution was linear in the concentration range 8.00×10^–6 to 5.00×10^–5 M. For iron(III) with larger sample volumes, the relative detection limit was increased. Most of the metals interfered negligibly, such as Ca(II), Co(II), Cu(II), Ni(II) and Zn(II), except for higher concentration of lead(II) and mercury(II) when present at up to 400 times the concentration of iron(III). The effects of EDTA, glycine, thiourea, phosphate, nitrate and chloride on the retention of iron(III) were also examined. Only thiourea significantly influenced the retention of iron(III). The presence of sodium chloride even at a concentration of 3.5×10⁴ times that of iron(III) did not interfere at all.

---

Bestimmung von Mikromengen Eisen durch Hydroxamatharz-Colorimetrie

     

A modified Mannich-type reaction catalyzed by VO(acac)(2)

A facile VO(acac)(2)-catalyzed in situ generation of iminium ions from amine N-oxides and their participation in a modified Mannich-type reaction is described.     

Asymmetric addition of dimethylzinc to alpha-ketoesters catalyzed by (-)-MITH

This investigation describes the catalytic asymmetric addition of dimethylzinc to alpha-ketoesters in the presence of (-)-MITH ( 5) and triethyl borate as an additive to give the corresponding chiral alpha-hydroxy esters with good yields and high enantioselectivities.