An efficient metal-templated route to C-functionalised derivatives of [12]aneN4

Abstract

The cyclo cocondensation of triethylenetetramine with arylpyruvaldehydes is templated by iron(m) chloride, to give a [ 12]aneN4 type diimine complex intermediate which may be reduced and demetallated in situ with sodium borohydride giving the saturated [ 12]aneN4 metal-free macrocycle in up to 60% overall yields; photophysical studies are used to demonstrate the similarity between the aryl functionalised [ 12]aneN4 derivatives formed by this route and analogues derived from [12]aneN4 itself.

Arylglyoxals in Synthesis of Heterocyclic Compounds

“…The reactions were carried out in dry methanol, followed by addition of excess NaBH 4 . Compounds 640 were transformed into the corresponding tetraacetate or tetramethylphosphinate derivatives 641 via reaction with ClCH 2 CO 2 – or with (CH 2 O) n –MeP(OEt) 2 followed by acidic hydrolysis (Scheme ) …”

“…Compounds 640 were transformed into the corresponding tetraacetate or tetramethylphosphinate derivatives 641 via reaction with ClCH 2 CO 2 − or with (CH 2 O) n −MeP(OEt) 2 followed by acidic hydrolysis (Scheme 194). 721 Nucleophilic trifluoromethylation of AG-imines with Ruppert−Prakash reagent (CF 3 SiMe 3 ) gave the corresponding Osilylated β-imino-α-(trifluoromethyl)alcohols, which underwent reduction and desilylation with NaBH 4 to yield the β-amino-α-(trifluoromethyl)alcohols 642. The β-amino alcohols 642 were used to synthesize diverse trifluoromethylated heterocycles, including aziridines 643, 1,3-oxazolidin-2-ones 644, 1,2,3oxathiazolidine 2-oxides 645, 1,3-oxazolidines 646, 1,3,2oxazaphospholidine 2-oxides 647, and morpholine-2,3-diones 648 as outlined in Scheme 195.…”

Chapter 20. The co-ordination chemistry of macrocyclic ligands

“…has been reported. 60 The key step is the reaction of an aryl glyoxal derivative [R(CO)CHO, prepared by the SeO, oxidation of aryl methyl ketones] with the complex cis-[FeCl,L']Cl (L' = triethylenetetramine), which is prepared in situ. The product of this reaction is the appropriate macrocyclic diimine, which is reduced in situ with sodium tetrahydroborate.…”

Anion and cation binding by a pendant arm cyclam and its macrobicyclic derivatives

“…This approach has been used highly successfully by Parker and co-workers for example, to develop a wide range of anion sensors based around lanthanoid complexes of the azamacrocycle cyclen ( [12]aneN 4 ). 16,17 Complexes of the larger cyclam ( [14]aneN 4 ) with pendant ammonium arms can bind nickel(II) within the macrocycle while hydrogen bonding to a coordinated anion via the pendant arms. 18 Extensive work by Gokel and co-workers has concentrated on alkali-metal cation complexation by lariat ethers and bibracchial lariat ethers (BiBLEs) in which the pendant arms contribute to cation binding even when the binding functional group is an alkene or alkyne.…”