Quantitative addition of organolithium and Grignard reagents to camphor (1) and fenchone (2) proceeds via precomplexation of the ketone with CeCl3 at room temperature. Excellent addition using catalytic or substoichiometric amounts of CeCl3 is demonstrated for the first time.

The new optically active 1,3-diols 5-8 with (1R)-(+)-camphor and (1R)-(-)-fenchone skeleton were synthesized in high yields from the homoallylic alcohols 1-4 using a very effective ozonolysis followed by reduction. The absolute configuration of (1R, 2S, 12R)-6a was determined by a single crystal X-ray study.

The aldehyde 3, prepared by ozonolysis of 2-allyl-2-nitrocyclododecanone, gave the ring-enlargement product 5 (85%) by treatment with (i-Bu)(2)AlH. Its transformation to the tetradecano-14-lactone (8) via the aldol ester 6 and other routes (best is reduction with Bu(3)SnH, AIBN, toluene) was difficult. Remarkable is the smooth denitrification of 3 (loss of HN0(2)) to the conjugated dione 4 by chromatography on silica gel or base treatment.

An improved strategy for synthesis of 1-chloro-bicyclo[2.2.2]octane is described in which the key compounds 1-norbornyl substituted ethyl formate (3) or 1-norbornylcarbaldehyde (7) were prepared from 1-norbornyllithium (1). The latter appeared as a useful precursor for the synthesis of various organic bridgehead substituted derivatives.

The new chiral nonracemic homoallylic exo-alcohols 6, 7, 10 with (1R)(+)-camphor (1) and endo-alcohols 8, 9, 11 with (1R)-(-)-fenchone (2) skeleton were synthesized in high yields by the stereoselective addition of allyl and substituted allylic Grignard reagents 3-5 to 1 and 2, respectively. The addition of the 2-butenyl (crotyl) reagent 5 occurred with high selectivity leading exclusively to alpha-methylallyl alcohol 10 with ketone 1 and to (Z)-2-butenyl alcohol 11 with ketone 2. The absolute configurations of the homoallylic alcohols 6-11 were determined by NMR methods.

The activity and efficiency of anhydrous CeCl3 depend strongly on the drying procedure. Deactivation of CeCl3 occurs during the drying process as a result of hydrolysis by the hydrate water, when heating above 90 degrees C. The highly active CeCl3, prepared by an improved drying procedure, is demonstrated to activate rapidly (in catalytic and stoichiometric amounts) ketones at room temperature, providing excellent addition of organometallic reagents. Copyright (C) 1996 Elsevier Science Ltd

New optically active aminoalcohols have been prepared from CeCl3-activated (+)-camphor and (-)-fenchone and N-functionalized organolithium compounds. The aminoalcohols obtained catalyze the addition of diethylzinc to benzaldehyde in high yields and enantioselectivities up to 64%. (C) 1997 Elsevier Science Ltd.

The allylic and homoallylic alcohols 1-8, prepared from (+)-camphor and (-)-fenchone, were ozonized in Et2O at -78 and treated with Et3N or LiAlH4 to give the chiral hydroxy carbonyl compounds 9-16 and the diols 17-24, respectively (Scheme I). In the case of the diols 19 and WI the formation of new chiral centers proceeded with high diastereoselectivity. These diols were prepared highly diastereoselectively also by LiAlH4 reduction of the hydroxy carbonyl compounds 11 and 16a, respectively (Scheme 2). The absolute configuration of the new chiral centers in 19 and 24 was determined by X-ray and NMR methods. The ozonization of compounds 2, 3, 7, and 8 provided the relatively stable hydroxy-substituted 1,2,4-trioxolane derivatives (ozonides) 37-40 (Scheme 5) which were characterized by H-1- and C-13-NMR spectra. ESI-MS, and natural-abundance O-17-NMR spectra.

New axially chiral steroidal binaphthols, prepared from estrone, were applied in the form of their Ti-alkoxides as catalysts for the addition of diethylzinc to aldehydes. The addition reactions proceeded with high yields and enantioselectivities up to 86%. (C) 2000 Elsevier Science Ltd. All rights reserved.

Detailed investigation of the tautomerism of oxazolidines, thiazolidines and selenazolidines substituted at positions 2 and 4 by hydroxy and amino groups was carried out by calculations at HF and MP2 levels of theory and NMR spectroscopy. The relative stabilities of the tautomers of the heterocycles were calculated in gas phase and in solvents CHCl3 and DMSO utilizing the PCM method. The ab initio calculations, in agreement with the available experimental data, predict that the azolidines substituted at positions 2 and 4 by a hydroxy and an amino group exist as amino form in solution, while 2,4-diamino-oxazolidine, -thiazolidine and -selenazolidine occur as mixtures of tautomers.