A stereodynamic chemosensor that can be used for simultaneous determination of the absolute configuration, enantiomeric composition and total concentration of chiral amines and amino alcohols based on two fast optical measurements was prepared and tested. The free sensor is CD-silent and produces characteristic blue-shifted UV and CD signals upon substrate binding via Schiff base formation. The...

We report the highly selective assembly of unprecedented eta5-1-methylene-1,2-dihydronaphthalenide ligands from the stoichiometric coupling of a phenyl group and two equivalents of disubstituted propargylic alcohols; in this reaction, tetraphenylborate acts as a phenylating agent.

Allylic and benzylic alcohols are converted into corresponding unsymmetrical ethers when reacted with various orthoesters in the presence of montmorillonite KSF at ambient temperature. A detailed study has been undertaken to examine the mechanism and generality of these reactions with regard to various acidic catalysts, which reveal interesting competitive reactions mainly O-acetylation, togeth...

Starting from pinane-, apopinane- and carane-based 1,3-amino alcohols obtained from monoterpene-based β-amino acids, a library of monoterpene-fused 2-imino-1,3-thiazines as main products and 2-thioxo-1,3-oxazines as side-products were prepared via two- or three-step syntheses. When thiourea adducts prepared from 1,3-amino alcohols and aryl isothiocyanates were reacted with CDI under mild condit...

[reaction: see text] Conformationally restricted amino alcohols based on carbohydrate scaffolds provide flexible and fine-tuneable libraries that greatly expand the range of ligands available in the Zn(OTf)(2)-mediated addition of alkynes to aldehydes, in some cases with very high stereoselectivities.

Cu-catalysed arylation reactions devoted to the formation of C-C and C-heteroatom bonds (Ullmann-type couplings) have acquired great importance in the last decade. This review discusses the history and development of coupling reactions between aryl halides and various classes of nucleophiles, focusing mostly on the different mechanisms proposed through the years. Selected mechanistic investigat...

A new strategy that employs an exocyclic stereocenter to effect diastereocontrol in the tethered aminohydroxylation (TA) reaction is applied to the stereoselective synthesis of a range of amino alcohols in good to excellent yields, and with anti selectivities of up to 20:1. The influence of the reaction conditions and substrate parameters on the level of diastereocontrol is described. Furthermo...

The unprecedented application of unmodified aldehydes as nucleophilic donors in direct catalytic asymmetric Mannich-type reactions is disclosed in a full account. Our efforts in broadening the applicability of chiral pyrrolidine-based catalysts in direct asymmetric Mannich-type reactions led to the highly diastereo- and enantioselective and concise synthesis of functionalized alpha- and beta-am...

An efficient methodology to oxidize benzylic and cinnamyl alcohols to their corresponding nitriles in excellent yields has been developed. This methodology employs DDQ as an oxidant and TMSN(3) as a source of nitrogen in the presence of a catalytic amount of Cu(ClO(4))(2)·6H(2)O.

A series of new octanuclear propeller-like aminoalcohol-supported Fe(III) oxocarboxylate coordination clusters, [Fe8O3(O2CCHMe2)9(tea)(teaH)3]·MeCN·2(H2O) (1), [Fe8O3(O2CCHMe2)6(N3)3(tea)(teaH)3] (2), [Fe8O3(O2CCMe3)6(N3)3(tea)(teaH)3]·0.5(EtOH) (3), and [Fe8O3(O2CCHMe2)6(N3)3(mdea)3(MeO)3] (4) (where teaH3 = triethanolamine; mdeaH2 = N-methyldiethanolamine) has been isolated and magnetochemica...