Spirobicyclic diamines. Part 3: Synthesis and metal complexation of proline-derived [4.4]-spirodiamines

Kelleher, Fintan; Kelly, Simon P.; McKee, Vickie

doi:10.1016/j.tet.2007.06.050

Cited by 10 publications

(8 citation statements)

References 28 publications

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“…Solid samples were prepared as dispersions in KBr discs and liquid samples as an interspersed film between polished sodium chloride plates. 5,11,17,arene (5) [20,21]. To calix [4]arene diacid 4 [12,13] (5.50 g, 7.19 mmol) in toluene (140 ml) was added thionyl chloride (0.41 ml, 7.4 mmol) and the solution was heated at reflux temperature for 2 h. After cooling, the solution was concentrated in vacuo to give a brown solid which was used without further purification (5.72 g, 99%).…”

Section: General Methodologymentioning

confidence: 99%

“…One method employed is the introduction of spirofused rings with defined conformational preferences due to the constraints imposed by their structure. We have reported previously on the synthesis, characterisation and binding properties of a number of proline-derived spirolactams and diamines [17][18][19]. The spirolactams were synthesised in good yields starting from L-proline …”

Section: Synthesismentioning

confidence: 99%

“…Spirolactam derivatised calixarene 7 was prepared in a similar manner to that described for 6 using trifluoroacetate salt 2 [17]. A mixture of diastereoisomers was recovered after purification by column chromatography in 5% methanol/dichloromethane to give an off white solid (0.62 g, 49%).…”

Section: 111723-tetra-tert-butyl-2527-di(7-allyl-6-oxo-17-diazamentioning

confidence: 99%

“…M.pt. 264-266 ºC; R f 0.21 (5% methanol/dichloromethane); 1 H NMR (CDCl 3 ,  ppm) 7.39 (s, 2H), 7.34-7.22 (m, 10H), 6.98 (s, 4H), 6.78 (s, 4H), 4.93-4.40 (m, 12H), 3.94-3.71 (m, 4H) 3.37-3.26 (m, 4H), 2.78-2.62 (m, 2H) 5,11,17,arene (10). To a solution of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix [4]arene [20,21,27] (4.0 g, 4.7 mmol) in THF (40 ml) was added sodium hydride (0.56 g, 23.5 mmol) and the mixture was stirred for 30 min at ambient temperature.…”

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

“…The solid residue was dissolved in dichloromethane (30 ml), washed with 10% aqueous HCl solution (10 ml), water (3 x 10 ml), dried over MgSO 4 and concentrated in vacuo. 5,11,17,28,dimethoxycalix[4]arene was recovered from methanol as a white solid (3.12 g, 74%). M.pt.…”

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

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Bis(spirolactam) 1,3-double-armed calix[4]arene compounds and their application as extractants for the determination of heavy metal ions

Ward

Regan

et al. 2015

J Incl Phenom Macrocycl Chem

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Section: General Methodologymentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Section: 111723-tetra-tert-butyl-2527-di(7-allyl-6-oxo-17-diazamentioning

confidence: 99%

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

Section: 111723-tetra-tert-butyl-2527-di(7-benzyl-6-oxo-17-diazmentioning

confidence: 99%

See 3 more Smart Citations

Bis(spirolactam) 1,3-double-armed calix[4]arene compounds and their application as extractants for the determination of heavy metal ions

Ward

Regan

et al. 2015

J Incl Phenom Macrocycl Chem

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Diastereodivergent Asymmetric Michael Addition of Cyclic Azomethine Ylides to Nitroalkenes: Direct Approach for the Synthesis of 1,7‐Diazaspiro[4.4]nonane Diastereoisomers

Yang

Luo

et al. 2015

Chemistry A European J

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The first highly diastereoselective and enantioselective catalytic asymmetric Michael addition of cyclic azomethine ylides with nitroalkenes have been developed to diastereodivergently generate either the syn or anti adducts by employing N,O-ligand/Cu(OAc)2 and N,P-ligand/Cu(OAc)2 catalytic systems. Both catalytic systems exhibit broad substrate applicability to afford the corresponding Michael adducts in good to excellent yields, with excellent levels of diastereo- (up to 99:1 diastereomeric ratio) and enantioselectivities (up to >99% enantiomeric excess). Importantly, the chiral 1,7-diazaspiro[4.4]nonane diastereomer derivatives can be easily obtained in good yields through facile NaBH4 reduction of the Michael adducts.

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Reductive amination of ferrocenylformylpyrazoles

et al. 2010

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1 Aryl 3 ferrocenyl 4 formylpyrazoles were obtained from appropriate acetylferrocene arylhydrazones by the Vilsmeier-Haack reaction. Direct reductive amination of the resulting aldehydes with primary and secondary amines and amino acid esters in the presence of NaBH(OAc) 3 was studied.Pyrazole derivatives exhibit a wide spectrum of phar macological activity. 1 Introduction of a ferrocenyl frag ment into a heterocyclic molecule often imparts a new biological activity to it or modifies its inherent activity. For instance, ferrocene containing pyrazoles have antibac terial 2 and antitumor effects in combination with low tox icity 3 and are plant growth regulators. 4 In addition, opti cally active ferrocenylpyrazole derivatives are suitable as ligands in asymmetric catalysis and can catalyze hydroge nation, silylation, and cyanation of carbonyl compounds. 5 In the present work, we studied direct reductive ami nation of 1 aryl 3 ferrocenylpyrazole 4 carbaldehydes in reactions with primary and secondary aliphatic amines. Results and DiscussionAryl methyl ketones are easily accessible reagents for the preparation of pyrazolecarbaldehydes. The synthesis involves condensation of ketones with arylhydrazines fol lowed by intramolecular cyclization of the resulting hydrazones under the conditions of the Vilsmeier-Haack formylation (Scheme 1).Reactions of acetylferrocene (1) with phenyl and β naphthylhydrazines gave the corresponding hydrazones in high yields, which were used in room temperature re actions with three equivalents of the Vilsmeier-Haack complex (DMF-POC1 3 ) in DMF. Upon hydrolysis of the iminium salts with aqueous Na 2 CO 3 , the correspond ing 1 aryl 3 ferrocenylpyrazole 4 carbaldehydes 2a,b were isolated in 84 and 65% yields, respectively.Aldehydes and ketones react with ammonia and pri mary and secondary amines in the presence of reducing agents to give primary, secondary, and tertiary amines, respectively. These reactions are known as reductive ami nation of carbonyl compounds or reductive alkylation of amines and can be effected in direct and stepwise ways. In the former case, a carbonyl compound and an amine are mixed with an appropriate reducing agent without isolating an intermediate imine or iminium salt. In the latter case, the formation of an intermediate imine is followed by its re duction. Secondary amines from pyrazolecarbaldehydes were obtained in the second way with sodium borohydride as a reducing agent, 6 while direct reductive amination of arylformylpyrazoles has not been implemented hitherto.Using sodium borohydride as a reducing agent in di rect reductive amination of 1 aryl 3 ferrocenylpyrazole 4 carbaldehydes in different solvents and at different tem peratures, we isolated the corresponding alcohols only. Modification of sodium borohydride with the electron withdrawing cyano or acetoxy group enhances the selec Scheme 1 Ar = Ph (a), β C 10 H 7 (b) Yield (%): 84 (2a), 65 (2b)

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Spirobicyclic diamines. Part 3: Synthesis and metal complexation of proline-derived [4.4]-spirodiamines

Abstract: The syntheses of racemic and homochiral

Cited by 10 publications

References 28 publications

Bis(spirolactam) 1,3-double-armed calix[4]arene compounds and their application as extractants for the determination of heavy metal ions

Bis(spirolactam) 1,3-double-armed calix[4]arene compounds and their application as extractants for the determination of heavy metal ions

Diastereodivergent Asymmetric Michael Addition of Cyclic Azomethine Ylides to Nitroalkenes: Direct Approach for the Synthesis of 1,7‐Diazaspiro[4.4]nonane Diastereoisomers

Reductive amination of ferrocenylformylpyrazoles

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