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The Mitsunobu alkylation of 4‐tert‐butylcalix[4]arene with (S)‐(2‐diphenylthiophosphinoferrocenyl)methanol followed by desulfuration of the thiophosphine unit using tris(dimethylamino)phosphine afforded enantiomerically pure calixarene mono‐ and di(ferrocenylphosphine) ligands in high yields. The calixarene mono(ferrocenylphosphine) ligands exhibited good catalytic activity but low atropoenantioselectivity when used in the asymmetric Suzuki–Miyaura coupling reaction of 1‐naphthaleneboronic acid and 1‐bromo‐2‐methylnaphthalene. However, the di(ferrocenylphosphine) ligand displayed both good catalytic activity and enantioselectivity (ee values up to 86 %) when employed in the asymmetric Tsuji–Trost allylic alkylation of 1,3‐diphenylprop‐2‐enyl acetate with dimethyl malonate.

A facile method for the preparation of enantiomerically pure inherently chiral calix[4]arene phosphonic acid (cR,pR)-7 in four steps starting from the readily available and previously synthesized (cS)-enantiomer of calix[4]arene acetic acid 1 or its methyl ester 2 was developed. The first tests of this unique calixarene Brönsted acid with inherent chirality in organocatalysis of the aza-Diels-Alder reaction of imines with Danishefsky's diene and epoxide ring opening by benzoic acid were performed. The calixarene phosphonic acid (cR,pR)-7 shows good catalytic activities but with low enantioselectivities in these reactions.

The synthetic approaches to mono-isopropoxytrihydroxycalix[4]arenes bearing two or three diphenylphosphino groups at the upper macrocycle rim were elaborated. Due to reactive hydroxyl groups at the lower rim capable of binding with silica gel surface, the calixarenes, especially the enantiomerically pure inherently chiral diphosphinocalixarene, are promissing ligands for creation of hybride organic -inorganic metallocomplexing catalysts of organic (asymmetric) reactions.

The reaction of 2-cyanomethylpyridine (I) with 1-chloroalkyl isocyanates (II), 1-chloroalkylcarbodiimides (V), 1,1-dichloroalkyl isocyanates (VII) as well as N-(1-chloroethylidene)-O-methylurethanes such as (IX) results in the formation of cyclization products having a pyrido[1,2-c]pyrimidine structure. -(VOVK, M. V.; LEBED, P. S.; CHERNEGA, A. N.; PIROZHENKO, V. V.; BOIKO, V. I.; TSYMBAL, I. F.; Chem.

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