Synthesis and characterization of symmetrical and unsymmetrical ferrocenyl ligands for use in the preparation of Redox Active Ruthenium Alkylidene Complexes
- Authors: Saku, Duduetsang
- Date: 2007
- Subjects: Ferrocene , Ligands , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10403 , http://hdl.handle.net/10948/701 , Ferrocene , Ligands , Asymmetric synthesis
- Description: Oxidation of a ferrocenyl group in conjugation to another metal centre can alter the electron density at that metal centre and lead to a change in overall reactivity of a complex. Herein, the synthesis and characterization of redox active symmetrical and unsymmetrical ferrocenylalkene derivatives is described. A change in the standard redox potential of ferrocene (465 mV), to more positive potentials in vinylferrocene 1 (478 mV) and 4-phenylvinylferrocene 3 (499 mV), showed how manipulation of a redox potential can be effected on the ferrocenyl moiety by just using conjugation effects. A shift by +13 mV is observed in 1 and this potential more than doubled in 3 (+34 mV). Ferrocenylderived ruthenium alkylidene complexes were also prepared in a cross metathesis of 1 and 3 with Grubbs’ 1 (676.5 mV) to give complexes Ferrocenylidenebis( tricyclohexylphosphine)dichlororuthenium 14, 4-ferrocenylphenylidene-bis (tricyclohexylphosphine)dichlororuthenium 15 respectively. The extent of the electronic communication between the ferrocenyl group and the ruthenium centre was then estimated by looking at the positive or negative redox potential shifts of 14 and 15 as a result of 1 and 3. A large positive potential shift by 180 mV in 14 indicated that there was a strong electronic communication between the two metal centres, while the smaller, yet significant positive potential shift by 89.5 mV in 15 showed 3 to have a lesser effect on the ruthenium centre. Compounds 14 and 15 were tested in a Ring Closing Metathesis (RCM) of diethyldiallylmalonate showed enhanced reactivity.
- Full Text:
- Date Issued: 2007
- Authors: Saku, Duduetsang
- Date: 2007
- Subjects: Ferrocene , Ligands , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:10403 , http://hdl.handle.net/10948/701 , Ferrocene , Ligands , Asymmetric synthesis
- Description: Oxidation of a ferrocenyl group in conjugation to another metal centre can alter the electron density at that metal centre and lead to a change in overall reactivity of a complex. Herein, the synthesis and characterization of redox active symmetrical and unsymmetrical ferrocenylalkene derivatives is described. A change in the standard redox potential of ferrocene (465 mV), to more positive potentials in vinylferrocene 1 (478 mV) and 4-phenylvinylferrocene 3 (499 mV), showed how manipulation of a redox potential can be effected on the ferrocenyl moiety by just using conjugation effects. A shift by +13 mV is observed in 1 and this potential more than doubled in 3 (+34 mV). Ferrocenylderived ruthenium alkylidene complexes were also prepared in a cross metathesis of 1 and 3 with Grubbs’ 1 (676.5 mV) to give complexes Ferrocenylidenebis( tricyclohexylphosphine)dichlororuthenium 14, 4-ferrocenylphenylidene-bis (tricyclohexylphosphine)dichlororuthenium 15 respectively. The extent of the electronic communication between the ferrocenyl group and the ruthenium centre was then estimated by looking at the positive or negative redox potential shifts of 14 and 15 as a result of 1 and 3. A large positive potential shift by 180 mV in 14 indicated that there was a strong electronic communication between the two metal centres, while the smaller, yet significant positive potential shift by 89.5 mV in 15 showed 3 to have a lesser effect on the ruthenium centre. Compounds 14 and 15 were tested in a Ring Closing Metathesis (RCM) of diethyldiallylmalonate showed enhanced reactivity.
- Full Text:
- Date Issued: 2007
Investigations into the asymmetric reduction of ketones
- Authors: Bena, Luvuyo Clifford
- Date: 2003
- Subjects: Ketones , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:11065 , http://hdl.handle.net/10948/323 , Ketones , Asymmetric synthesis
- Description: A six-step synthesis of salbutamol from methyl salicylate with an overall yield of 17% has been completed, although the yield was not optimised. In the process, Zn(BH4)2 was found to selectively reduce a ketone carbonyl group in the presence of an ester unit. In contrast, borane was found to reduce both the ketone and ester carbonyl groups. Reduction of phenacyl bromide with borane in the presence of chiral catalysts based on (R)-alaninol and (R,S)-ephidrine resulted a measure of enantioselectivity in the product. However, the configuration of the alcohol obtained in the case of (R)-alaninol was contrary to expectations based both on experimental trends observed elsewhere as well as our own theoretical predictions. The asymmetric reduction of methyl 5-bromoacetyl-2-benzyloxybenzoate was accomplished with both borane and Zn(BH4)2 in the presence of a range of chiral catalysts. Optically active products were obtained in all cases, although the optical rotations were significantly smaller in the case of Zn(BH4)2. Unfortunately, we were not successful in determining the enantiomeric excesses of these reactions. The use of a NMR lanthanide shift reagent resulted in a complex spectrum that was impossible to interpret unambiguously. This presumably arises from the presence of several Lewis base sites in the product at which complexation with the shift reagent can take place. It was also not possible to determine the optical rotation of salbutamol itself owing to the relatively small amount of material obtained. A conformational analysis of salbutamol, where NMR data was correlated with molecular modelling results, was successfully carried out and revealed a strong preference for that conformer family characterised by O–C–C–N and Ar–C–C–N torsion angles of ca. 60º and 180º, respectively. Interestingly, these conformers are found to be stabilised by OH…N rather than NH…O hydrogen bonding. This study has also confirmed the effectiveness of the MMFF94 force field for conformational analysis studies in compounds of this kind. Lastly, a relatively simple method for modelling the BH3/oxazaborolidine reduction of ketones at the PM3 semiempirical MO level of approximation was devised. This approach has provided insights into the mechanism of the reaction and has furthermore enabled us to predict the enantioselectivities likely to result from various catalysts and ketones. In comparing our theoretical and experimental findings, an anomalous result was observed in the case of (R)-alaninol; this will have to be investigated further, particularly at the experimental level. However, we believe that our approach provides a sound basis for aiding the design and screening of new, potentially better catalysts.
- Full Text:
- Date Issued: 2003
- Authors: Bena, Luvuyo Clifford
- Date: 2003
- Subjects: Ketones , Asymmetric synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:11065 , http://hdl.handle.net/10948/323 , Ketones , Asymmetric synthesis
- Description: A six-step synthesis of salbutamol from methyl salicylate with an overall yield of 17% has been completed, although the yield was not optimised. In the process, Zn(BH4)2 was found to selectively reduce a ketone carbonyl group in the presence of an ester unit. In contrast, borane was found to reduce both the ketone and ester carbonyl groups. Reduction of phenacyl bromide with borane in the presence of chiral catalysts based on (R)-alaninol and (R,S)-ephidrine resulted a measure of enantioselectivity in the product. However, the configuration of the alcohol obtained in the case of (R)-alaninol was contrary to expectations based both on experimental trends observed elsewhere as well as our own theoretical predictions. The asymmetric reduction of methyl 5-bromoacetyl-2-benzyloxybenzoate was accomplished with both borane and Zn(BH4)2 in the presence of a range of chiral catalysts. Optically active products were obtained in all cases, although the optical rotations were significantly smaller in the case of Zn(BH4)2. Unfortunately, we were not successful in determining the enantiomeric excesses of these reactions. The use of a NMR lanthanide shift reagent resulted in a complex spectrum that was impossible to interpret unambiguously. This presumably arises from the presence of several Lewis base sites in the product at which complexation with the shift reagent can take place. It was also not possible to determine the optical rotation of salbutamol itself owing to the relatively small amount of material obtained. A conformational analysis of salbutamol, where NMR data was correlated with molecular modelling results, was successfully carried out and revealed a strong preference for that conformer family characterised by O–C–C–N and Ar–C–C–N torsion angles of ca. 60º and 180º, respectively. Interestingly, these conformers are found to be stabilised by OH…N rather than NH…O hydrogen bonding. This study has also confirmed the effectiveness of the MMFF94 force field for conformational analysis studies in compounds of this kind. Lastly, a relatively simple method for modelling the BH3/oxazaborolidine reduction of ketones at the PM3 semiempirical MO level of approximation was devised. This approach has provided insights into the mechanism of the reaction and has furthermore enabled us to predict the enantioselectivities likely to result from various catalysts and ketones. In comparing our theoretical and experimental findings, an anomalous result was observed in the case of (R)-alaninol; this will have to be investigated further, particularly at the experimental level. However, we believe that our approach provides a sound basis for aiding the design and screening of new, potentially better catalysts.
- Full Text:
- Date Issued: 2003
Asymmetric α-alkylation reactions
- Authors: Klein, Rosalyn
- Date: 2000
- Subjects: Asymmetric synthesis , Alkylation , Chemical reactions
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4405 , http://hdl.handle.net/10962/d1006710 , Asymmetric synthesis , Alkylation , Chemical reactions
- Description: A novel camphor-derived hydroxy ketal 138 has been developed as a crural auxiliary, and used to prepare a series of six carboxylic esters of increasing steric bulk. The α-benzylation of this series of esters was achieved with diastereoselectivities of 59 - 83% d. e. and in 39 - 48% material yield. These results compared very favourably with those obtained in earlier studies using a regioisomeric analogue as the chiral auxiliary. Computer.modelling studies of the putative enolate intermediate has provided some insight into the possible mode of electrophilic attack at the α-carbon and the roles of the ketal protecting group and the lithium cation in these asymmetric transformations. In a related investigation, based on earlier work, a camphor-derived imino lactone has provided convenient access to α-alkyl α-amino acids, the imino lactone serving as a masked glycine equivalent. Using straight chain primary alkyl iodides [RI; R = Me, Et, Pr, Bu, CH₃(CH₂)₄ and CH₃(CH₄)₅], alkylation of the potassium enolate of the camphor-derived imino lactone was effected with 54 - 89% d.e. and in 54 - 87% material yield. Four novel alkylated derivatives were synthesised using isopropyl iodide, sec-butyl iodide and allyl iodide, the latter reagent resulting in both the monoallylated and diallylated products. While very good diastereoselectivities were achieved (83 - 88% d. e.) in these reactions, the material yields from reaction with the secondary alkyl iodides were low (31- 35%) due, presumably, to their decreased electrophilicity. Computer modelling studies of the enolate were carried out and support the hypothesis of endo attack by the electrophile on the enolate intermediate. These studies also indicate the possibility of coordination of the postassium cation to the endocyclic ester oxygen, thus effectively anchoring the bulky cation away from the reaction site.
- Full Text:
- Date Issued: 2000
- Authors: Klein, Rosalyn
- Date: 2000
- Subjects: Asymmetric synthesis , Alkylation , Chemical reactions
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4405 , http://hdl.handle.net/10962/d1006710 , Asymmetric synthesis , Alkylation , Chemical reactions
- Description: A novel camphor-derived hydroxy ketal 138 has been developed as a crural auxiliary, and used to prepare a series of six carboxylic esters of increasing steric bulk. The α-benzylation of this series of esters was achieved with diastereoselectivities of 59 - 83% d. e. and in 39 - 48% material yield. These results compared very favourably with those obtained in earlier studies using a regioisomeric analogue as the chiral auxiliary. Computer.modelling studies of the putative enolate intermediate has provided some insight into the possible mode of electrophilic attack at the α-carbon and the roles of the ketal protecting group and the lithium cation in these asymmetric transformations. In a related investigation, based on earlier work, a camphor-derived imino lactone has provided convenient access to α-alkyl α-amino acids, the imino lactone serving as a masked glycine equivalent. Using straight chain primary alkyl iodides [RI; R = Me, Et, Pr, Bu, CH₃(CH₂)₄ and CH₃(CH₄)₅], alkylation of the potassium enolate of the camphor-derived imino lactone was effected with 54 - 89% d.e. and in 54 - 87% material yield. Four novel alkylated derivatives were synthesised using isopropyl iodide, sec-butyl iodide and allyl iodide, the latter reagent resulting in both the monoallylated and diallylated products. While very good diastereoselectivities were achieved (83 - 88% d. e.) in these reactions, the material yields from reaction with the secondary alkyl iodides were low (31- 35%) due, presumably, to their decreased electrophilicity. Computer modelling studies of the enolate were carried out and support the hypothesis of endo attack by the electrophile on the enolate intermediate. These studies also indicate the possibility of coordination of the postassium cation to the endocyclic ester oxygen, thus effectively anchoring the bulky cation away from the reaction site.
- Full Text:
- Date Issued: 2000
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