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Papers by robert filik
Abbreviations xxii Chapter 1 1.4.3 O-benzoyl hydroxamic acid derivatives 39 References 41 Chapter... more Abbreviations xxii Chapter 1 1.4.3 O-benzoyl hydroxamic acid derivatives 39 References 41 Chapter 2 Investigation into the stereochemistry of 5-exo cyclisations of amidyl radical cyclisation 2.1 Introduction 47 2.2 Precursor selection 49 2.2.1 Choice of precursors 2.2.2 Preparation o f precursors (78)-(82), method 1 2.2.3 Manipulation o f hydroxamic acids (78-82) to the O-benzoyl protected versions (83-88) 2.2.4 Preparation of precursors (89) and (90), method 2 2.2.5 Summary 2.2.6 l3C Spectra 2.3 Cyclisation reactions 2.3.1 Cyclisations o f methyl pendant precursors 2.3.2 Cyclisations o f methyl pendant precursors 2.4 Discussions and conclusions 2.5 Future work Chapter 3 New alternative methods for generating amidyl radicals 3.1 8.2.1 Stereochemical assignment 8.3 Cyclisation of AT-allyl-4-toluenesulfonyl-2-bromoacetamide (126) 141 8.4 Conclusions 8.5 Future work References Chapter 9 Experimental Experimental Notes 9.1 Experimental for chapter 2 9.1.1 Acid synthesis 9.1.1.1 2-Allyl-2-methylmalonic acid diethyl ester (72) 149 9.1.1.2 2-Allyl-2-methylmalonic acid (73) 150 9.1.1.3 2-Methyl-pent-4-enoic acid (74) 150 9.1.1.4 2-Allyl-2-phenylmalonic acid diethyl ester (75) 151 9.1.1.5 2-Phenyl-pent-4-enoic acid (76) 152 9.1.2 AT-Alkyl-AT-benzoyloxy-2-methyI pent-4-enamides (Method 1) 9.1.2.1 AT-Benzyl-AT-hydroxyl-2-methyl pent-4-enamide (78) 9.1.2.2 AT-Benzoyloxy-A-benzyl-2-methyl pent-4-enamide (83) 9.1.2.3 TV-Hydroxyl-/V-/-propyl-2-methyl pent-4-enamide (79) 9.1.2.4 /V-Benzoyloxy-iV-/-propyl-2-methyl pent-4-enamide (84) 9.1.2.5 AT-Benzoyloxy-AT-methyl-2-methyl pent-4-enamide (85) 9.1.3 AT-Alkyl-AT-benzoyloxy-2-phenyl pent-4-enamides (Method 1) 9.1.3.1 AT-Benzyl-AT-hydroxyl-2-phenyl pent-4-enamide (80) 9.1.3.2 AT-Benzyloxy-AT-benzyl-2-phenyl pent-4-enamide (86) 9.1.3.3 AT-Hydroxyl-AT-methyl-2-phenyl pent-4-enoic acid (81) 9.1.3.4 AT-Benzyloxy-A-methyl-2-phenyl pent-4-enamide (87) 161 9.1.3.5 AT-Hydroxyl-AT-/-propyl-2-phenyl pent-4-enamide (82) 162-vi-9.1.3.6 Af-Benzoyloxy-jV-/'-propyl-2-phenyl pent-4-enamide (88) 163 9.1.4 Af-n-Butyl-Ar-benzoyloxy-2-methyl pent-4-enamide (Method 2) 164 9.1.4.1 A,-M-Butyl-/V-benzoyloxy-2-methyl pent-4-enamide (89) 9.1.4.2 N-n-Butyl-/V-benzoyloxy-2-phenyl pent-4-enamide (90) 9.1.5 3,5-Di-substituted pyrrolidinones 9.1.5.1 N-Benzyl-3,5-dimethyl pyrrolidin-2-one (91) 166 9.1.5.2 jV-z-Propyl-3,5-dimethyl pyrrolidin-2-one (92) 9.1.5.3 N-Methyl-3,5-dimethyl pyrrolidin-2-one (93) 9.1.5.4 N-n-Butyl-3,5-dimethyl pyrrolidin-2-one (94) 9.
John Wiley & Sons, Ltd eBooks, Apr 2, 2003
O-benzoyl hydroxamic acids were found to be suitable precursors for the generation of amidyl radi... more O-benzoyl hydroxamic acids were found to be suitable precursors for the generation of amidyl radicals. A stereoselectivity study was performed to investigate the 5-exo cyclisations of the amidyl radicals formed. Hence a range of methyl and phenyl 2- substituted N-alkyl-Af-benzoyloxy-pent-4-enamides were synthesised and cyclised using tributyltin hydride and AIBN. A small preference for the Irons isomer was observed in all cases (10-36%) with the phenyl pendant series giving the highest selectivities. The observed Irons isomer was not that expected by current theories (Beckwith and Houk model). The effect of the N-substituent was found to exert little or no influence on the stereoselectivity of any of the reactions. Due to the difficulties in removing toxic tin residues from the reaction mixture alternative methods for the generation and 5-exo cyclisation of amidyl radicals utilising A-acyl hydroxamic acids were investigated using Cu(OTf)2 and Sml2. The effect of concentration, solve...
ChemInform
ring closure reactions ring closure reactions O 0130 31-060 N-Alkyl-2-pyridylmethanimines as Tune... more ring closure reactions ring closure reactions O 0130 31-060 N-Alkyl-2-pyridylmethanimines as Tuneable Alternatives to Bipyridine Ligands in Copper-Mediated Atom Transfer Radical Cyclization.-α,α,α-Trichloroallylacetate (I) is found to undergo efficient atom transfer radical cyclization to the lactone (II) in the presence of copper halide complexes of N-alkyl-2-pyridylmethanimine (conditions B). Under similar conditions, deactivated (III) and unactivated α-haloallylacetamides (VI) react analogously to the lactams (IV)/(V) and (VII) in good yield.-(CLARK, ANDREW
Tetrahedron Letters, Jul 1, 2013
ABSTRACT
The Journal of Organic Chemistry, Nov 2, 1999
... Nitin T. Patil and Yoshinori Yamamoto. Chemical Reviews 2008 108 (8), 3395-3442. ... Synthesi... more ... Nitin T. Patil and Yoshinori Yamamoto. Chemical Reviews 2008 108 (8), 3395-3442. ... Synthesis, Structure, and Reactivity of the Methoxy-Bridged Dimer [Cp Ru(μ-OMe)] 2 (Cp = η 5 -1-Methoxy-2,4-di-tert-butyl-3-neopentylcyclopentadienyl). Barnali Dutta, Rosario Scopelliti and ...
Synlett, 1999
© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journa... more © Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or ...
ChemInform, 1999
ring closure reactions ring closure reactions O 0130 31-059 Tandem Cyclization of Amidyl Radicals... more ring closure reactions ring closure reactions O 0130 31-059 Tandem Cyclization of Amidyl Radicals Derived from O-Acyl Hydroxamic Acid Derivatives.-An approach to biologically active bicyclic and tricyclic nitrogen heterocycles is investigated. Tributylstannane/AIBNmediated homolysis of O-acyl hydroxamic acid derivatives (I) and (V) gives amidyl radicals which undergo tandem cyclization, monocyclization, and direct reduction reactions. A similar behavior is observed when Cu(O-Tf) 2 /DBN is employed.-(CLARK,
Journal of the Chemical Society, Perkin Transactions 1, 2000
In recent years, transition metal mediated free radical processes have gained in importance.1 In ... more In recent years, transition metal mediated free radical processes have gained in importance.1 In particular the atom transfer radical cyclisation reactions (ATRC) of 2,2,2-trichlorinated carbonyl compounds have been reported with a range of metal catalysts, eg RuCl 2 (PPh 3 ) 3 ,2 ...
ChemInform, 2000
Solid-Supported Catalysts for Atom-Transfer Radical Cyclization of 2-Haloacetamides.-It is shown ... more Solid-Supported Catalysts for Atom-Transfer Radical Cyclization of 2-Haloacetamides.-It is shown that copper(I) halide complexes of silica-supported ligands are efficient catalysts for the cyclization of activated and unactivated 2-haloacetamides.-(CLARK,
Tetrahedron Letters, 1999
The relative rate of copper (I) mediated atom U'ansfer radical cyclisation of (11) with a range o... more The relative rate of copper (I) mediated atom U'ansfer radical cyclisation of (11) with a range of ligands at room temperature has been screened. The most active ligands were found to be multidentate amine ligands (6-7).
Tetrahedron Letters, 2013
ABSTRACT
Tetrahedron Letters, 1999
Copper halide complexes of N-alkyl-2-pyridylmcthanimines (3, 11-14) catalyse atom transfer radica... more Copper halide complexes of N-alkyl-2-pyridylmcthanimines (3, 11-14) catalyse atom transfer radical cyclisation reactions of activated (6a-b) and unactivated oc-haloallylacetamides (9) at room temperature.
Tetrahedron Letters, 1998
Pergamon Tetrahedron Letters 39 (1998) 12691272 TETRAHEDRON LETTERS Rearrangements of Activated O... more Pergamon Tetrahedron Letters 39 (1998) 12691272 TETRAHEDRON LETTERS Rearrangements of Activated OAcyi Hydroxamic Acid Derivatives. Yasair SS A1Faiyz", Andrew J. Clark*", Robert P. Filika, Joanne. L. Peacocka, and Gerry H. Thomasb a) Department of Chemistry, ...
Synlett, 1999
© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journa... more © Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or ...
Abbreviations xxii Chapter 1 1.4.3 O-benzoyl hydroxamic acid derivatives 39 References 41 Chapter... more Abbreviations xxii Chapter 1 1.4.3 O-benzoyl hydroxamic acid derivatives 39 References 41 Chapter 2 Investigation into the stereochemistry of 5-exo cyclisations of amidyl radical cyclisation 2.1 Introduction 47 2.2 Precursor selection 49 2.2.1 Choice of precursors 2.2.2 Preparation o f precursors (78)-(82), method 1 2.2.3 Manipulation o f hydroxamic acids (78-82) to the O-benzoyl protected versions (83-88) 2.2.4 Preparation of precursors (89) and (90), method 2 2.2.5 Summary 2.2.6 l3C Spectra 2.3 Cyclisation reactions 2.3.1 Cyclisations o f methyl pendant precursors 2.3.2 Cyclisations o f methyl pendant precursors 2.4 Discussions and conclusions 2.5 Future work Chapter 3 New alternative methods for generating amidyl radicals 3.1 8.2.1 Stereochemical assignment 8.3 Cyclisation of AT-allyl-4-toluenesulfonyl-2-bromoacetamide (126) 141 8.4 Conclusions 8.5 Future work References Chapter 9 Experimental Experimental Notes 9.1 Experimental for chapter 2 9.1.1 Acid synthesis 9.1.1.1 2-Allyl-2-methylmalonic acid diethyl ester (72) 149 9.1.1.2 2-Allyl-2-methylmalonic acid (73) 150 9.1.1.3 2-Methyl-pent-4-enoic acid (74) 150 9.1.1.4 2-Allyl-2-phenylmalonic acid diethyl ester (75) 151 9.1.1.5 2-Phenyl-pent-4-enoic acid (76) 152 9.1.2 AT-Alkyl-AT-benzoyloxy-2-methyI pent-4-enamides (Method 1) 9.1.2.1 AT-Benzyl-AT-hydroxyl-2-methyl pent-4-enamide (78) 9.1.2.2 AT-Benzoyloxy-A-benzyl-2-methyl pent-4-enamide (83) 9.1.2.3 TV-Hydroxyl-/V-/-propyl-2-methyl pent-4-enamide (79) 9.1.2.4 /V-Benzoyloxy-iV-/-propyl-2-methyl pent-4-enamide (84) 9.1.2.5 AT-Benzoyloxy-AT-methyl-2-methyl pent-4-enamide (85) 9.1.3 AT-Alkyl-AT-benzoyloxy-2-phenyl pent-4-enamides (Method 1) 9.1.3.1 AT-Benzyl-AT-hydroxyl-2-phenyl pent-4-enamide (80) 9.1.3.2 AT-Benzyloxy-AT-benzyl-2-phenyl pent-4-enamide (86) 9.1.3.3 AT-Hydroxyl-AT-methyl-2-phenyl pent-4-enoic acid (81) 9.1.3.4 AT-Benzyloxy-A-methyl-2-phenyl pent-4-enamide (87) 161 9.1.3.5 AT-Hydroxyl-AT-/-propyl-2-phenyl pent-4-enamide (82) 162-vi-9.1.3.6 Af-Benzoyloxy-jV-/'-propyl-2-phenyl pent-4-enamide (88) 163 9.1.4 Af-n-Butyl-Ar-benzoyloxy-2-methyl pent-4-enamide (Method 2) 164 9.1.4.1 A,-M-Butyl-/V-benzoyloxy-2-methyl pent-4-enamide (89) 9.1.4.2 N-n-Butyl-/V-benzoyloxy-2-phenyl pent-4-enamide (90) 9.1.5 3,5-Di-substituted pyrrolidinones 9.1.5.1 N-Benzyl-3,5-dimethyl pyrrolidin-2-one (91) 166 9.1.5.2 jV-z-Propyl-3,5-dimethyl pyrrolidin-2-one (92) 9.1.5.3 N-Methyl-3,5-dimethyl pyrrolidin-2-one (93) 9.1.5.4 N-n-Butyl-3,5-dimethyl pyrrolidin-2-one (94) 9.
John Wiley & Sons, Ltd eBooks, Apr 2, 2003
O-benzoyl hydroxamic acids were found to be suitable precursors for the generation of amidyl radi... more O-benzoyl hydroxamic acids were found to be suitable precursors for the generation of amidyl radicals. A stereoselectivity study was performed to investigate the 5-exo cyclisations of the amidyl radicals formed. Hence a range of methyl and phenyl 2- substituted N-alkyl-Af-benzoyloxy-pent-4-enamides were synthesised and cyclised using tributyltin hydride and AIBN. A small preference for the Irons isomer was observed in all cases (10-36%) with the phenyl pendant series giving the highest selectivities. The observed Irons isomer was not that expected by current theories (Beckwith and Houk model). The effect of the N-substituent was found to exert little or no influence on the stereoselectivity of any of the reactions. Due to the difficulties in removing toxic tin residues from the reaction mixture alternative methods for the generation and 5-exo cyclisation of amidyl radicals utilising A-acyl hydroxamic acids were investigated using Cu(OTf)2 and Sml2. The effect of concentration, solve...
ChemInform
ring closure reactions ring closure reactions O 0130 31-060 N-Alkyl-2-pyridylmethanimines as Tune... more ring closure reactions ring closure reactions O 0130 31-060 N-Alkyl-2-pyridylmethanimines as Tuneable Alternatives to Bipyridine Ligands in Copper-Mediated Atom Transfer Radical Cyclization.-α,α,α-Trichloroallylacetate (I) is found to undergo efficient atom transfer radical cyclization to the lactone (II) in the presence of copper halide complexes of N-alkyl-2-pyridylmethanimine (conditions B). Under similar conditions, deactivated (III) and unactivated α-haloallylacetamides (VI) react analogously to the lactams (IV)/(V) and (VII) in good yield.-(CLARK, ANDREW
Tetrahedron Letters, Jul 1, 2013
ABSTRACT
The Journal of Organic Chemistry, Nov 2, 1999
... Nitin T. Patil and Yoshinori Yamamoto. Chemical Reviews 2008 108 (8), 3395-3442. ... Synthesi... more ... Nitin T. Patil and Yoshinori Yamamoto. Chemical Reviews 2008 108 (8), 3395-3442. ... Synthesis, Structure, and Reactivity of the Methoxy-Bridged Dimer [Cp Ru(μ-OMe)] 2 (Cp = η 5 -1-Methoxy-2,4-di-tert-butyl-3-neopentylcyclopentadienyl). Barnali Dutta, Rosario Scopelliti and ...
Synlett, 1999
© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journa... more © Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or ...
ChemInform, 1999
ring closure reactions ring closure reactions O 0130 31-059 Tandem Cyclization of Amidyl Radicals... more ring closure reactions ring closure reactions O 0130 31-059 Tandem Cyclization of Amidyl Radicals Derived from O-Acyl Hydroxamic Acid Derivatives.-An approach to biologically active bicyclic and tricyclic nitrogen heterocycles is investigated. Tributylstannane/AIBNmediated homolysis of O-acyl hydroxamic acid derivatives (I) and (V) gives amidyl radicals which undergo tandem cyclization, monocyclization, and direct reduction reactions. A similar behavior is observed when Cu(O-Tf) 2 /DBN is employed.-(CLARK,
Journal of the Chemical Society, Perkin Transactions 1, 2000
In recent years, transition metal mediated free radical processes have gained in importance.1 In ... more In recent years, transition metal mediated free radical processes have gained in importance.1 In particular the atom transfer radical cyclisation reactions (ATRC) of 2,2,2-trichlorinated carbonyl compounds have been reported with a range of metal catalysts, eg RuCl 2 (PPh 3 ) 3 ,2 ...
ChemInform, 2000
Solid-Supported Catalysts for Atom-Transfer Radical Cyclization of 2-Haloacetamides.-It is shown ... more Solid-Supported Catalysts for Atom-Transfer Radical Cyclization of 2-Haloacetamides.-It is shown that copper(I) halide complexes of silica-supported ligands are efficient catalysts for the cyclization of activated and unactivated 2-haloacetamides.-(CLARK,
Tetrahedron Letters, 1999
The relative rate of copper (I) mediated atom U'ansfer radical cyclisation of (11) with a range o... more The relative rate of copper (I) mediated atom U'ansfer radical cyclisation of (11) with a range of ligands at room temperature has been screened. The most active ligands were found to be multidentate amine ligands (6-7).
Tetrahedron Letters, 2013
ABSTRACT
Tetrahedron Letters, 1999
Copper halide complexes of N-alkyl-2-pyridylmcthanimines (3, 11-14) catalyse atom transfer radica... more Copper halide complexes of N-alkyl-2-pyridylmcthanimines (3, 11-14) catalyse atom transfer radical cyclisation reactions of activated (6a-b) and unactivated oc-haloallylacetamides (9) at room temperature.
Tetrahedron Letters, 1998
Pergamon Tetrahedron Letters 39 (1998) 12691272 TETRAHEDRON LETTERS Rearrangements of Activated O... more Pergamon Tetrahedron Letters 39 (1998) 12691272 TETRAHEDRON LETTERS Rearrangements of Activated OAcyi Hydroxamic Acid Derivatives. Yasair SS A1Faiyz", Andrew J. Clark*", Robert P. Filika, Joanne. L. Peacocka, and Gerry H. Thomasb a) Department of Chemistry, ...
Synlett, 1999
© Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journa... more © Georg Thieme Verlag, Rüdigerstr. 14, 70469 Stuttgart, Germany. All rights reserved. This journal, including all individual contributions and illustrations published therein, is legally protected by copyright for the duration of the copyright period. Any use, exploitation or ...