This thesis describes work towards a range of novel nitrogen containing polyaromatic heterocycles for use as organic semiconductors. A route to benzo[b]carbazole end-capped oligothiophenes has been developed; relying on two key steps; namely a connective-Pummerer cyclisation and a SmI2-mediated cleavage–cyclisation cascade. A route to extended dibenzoindolo[3,2-b]carbazole-based aza-heptacenes has also been developed, by employing the same key steps in a two-directional manner. The physical and electronic properties of the resulting materials has been assessed, and the utility of the materials in OFET devices has been demonstrated.

No description available.

No description available.

A connective Pummerer reaction was developed with a view to its use in the synthesis of analogues of ecteinascidin 597, a member of a family of potent anti-tumour natural products. A one-step synthesis of N-benzyl 2-hydroxyamides, involving the reaction of 2,2-dimethyl-1,3-dioxolan-4-one with amines, was investigated and the products were oxidised to give glyoxamides. Reaction conditions were optimised for the cyclisation of electron-rich N-benzyl glyoxamides in the presence of thiols and a Lewis acid (ZnCl2 or Sc(OTf)3) to give 4-sulfanyltetrahydroisoquinolinones, and mechanistic studies indicated the importance of hemithioacetal and thionium intermediates in these reactions. The scope of the reaction was found to encompass electron-rich N-benzyl pyruvamide substrates, which gave 4-methyl-4-sulfanyltetrahydroisoquinolinone products via what is believed to be a combination of thionium ion and cyclisation-substitution pathways. Under more forcing conditions, connective Pummerer cyclisation of N-benzyl 2,2-diethoxyacetamides was successful. Sharpless asymmetric aminohydroxylation and a Sharpless asymmetric dihydroxylation-Mitsunobu sequence were exploited in the synthesis of an enantioenriched 1,2-aminoalcohol. Subsequent conversion to branched, N-benzyl 2-hydroxyacetamides by PMB and silyl protection and N-acylation then oxidation and cyclisation furnished 1-silyloxymethyl-4-sulfanyl tetrahydroisoquinolinones. Modification of these tetrahydroisoquinolinones gave bridged macrolactones which map onto the A subunit of the ecteinascidins. A one-pot macrolactone synthesis using a connective Pummerer reaction was unsuccessfully attempted on a substrate bearing 2,2-diethoxyacetamide and thiol moiety in addition to an electron-rich benzene ring. A new protecting group strategy was necessary for continuation of the analogue synthesis and a variety of N,O-acetals were evaluated for the protection of the 1,2-aminoalcohol.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14581号 / 工博第3049号 / 新制||工||1454(附属図書館) / 26933 / UT51-2009-D293 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 大嶌 幸一郎, 教授 檜山 爲次郎, 教授 松原 誠二郎 / 学位規則第4条第1項該当

Treatment of 1-(methylsulfinyl)-2-(phenylethynyl)benzene with 10 mol % of mercury dichloride and 1 equivalent of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in refluxing benzene gave benzo[b]thiophene in good yields. This method tolerated various functional groups in phenylethynyl moiety, including electron donating groups and electron withdrawing groups. Useing 1-(benzylsulfinyl)-2-(phenylethynyl)benzene as reaction substrate increased the yields of benzo[b]thiophene derivatives. Isotope effect showed that this cyclization reaction belong to Pummerer type cyclization reaction.

A finalidade deste trabalho é o estudo de reações de carbânions de sulfóxidos funcionalizados com reagentes sulfenilantes, pelo emprego de dois métodos: fase homogênea e transferência de fases. A revisão bibliográfica apresentada demonstra que trata-se de reações novas e que, entretanto, outras reações de carbânions de sulfóxidos funcionalizados, tais como alquilações, acilações, condensações com compostos carbonílicos e adições de Michael, já tinham sido descritas. Por outro lado, poucas reações de sulfinil carbânions tinham sido efetuadas pelo emprego do método de transferência de fases. As reações de sulfenilação em fase homogênea de α-sulfinil cetonas aromáticas (Ia-d), e cíclicas (II), α-sulfinil ésteres (IIIa,b) e tioéster (IV) foram efetuadas pelo emprego de NaH/DMSO e de dimetildissulfeto ou metanotiossulfonato de metila (MeSO2SMe). Com exceção do composto (IIIb) que não reagiu, em todos os casos foram obtidos compostos monossulfenilados ainda não descritos na literatura. Os rendimentos variavam entre 25-90%, na ordem: Ib > Ia > IVa > Ic > Id > IIIa > II. As reações de sulfenilação em transferência de fases foram efetuadas pelo emprego de dois procedimentos distintos: o de extração do íon-par (A) e o sistema Sólido-líquido (B). Os compostos Ia, IIIa e IVb foram submetidos à sulfenilação pelo procedimento A, em que usou-se NaOH/CH2Cl2/Bu4NHSO4 e MeSO2SMe. Enquanto Ia e IIIa renderam produtos monossulfenilados em baixos rendimentos, IVb não reagiu. As reações de sulfenilação pelo procedimento B, usando-se K2CO3/ΦH/TEBA e MeSO2SMe foram efetuadas com os compostos Ia-d, IIIa e IVb e mostraram-se mais satisfatórias do que pelo procedimento A, pois todos reagiram, rendendo produtos monossulfenilados. O rendimento do composto IIIa era apenas de 20% , mas os rendimentos dos outros derivados variavam entre 40-67%. Observou-se, através da análise de RMN-1H, em todos os derivados sulfenilados, a presença de dois diastereoisômeros em quantidades iguais. Entretanto, substituindo-se o TEBA por um sal de quinínio quirálico, no caso de duas sulfinil cetonas (Ia e Ic) os compostos sulfenilados correspondentes mostraram uma relação diastereomérica de 4:1. O trabalho apresenta também os resultados de decomposição térmica de sulfinil cetonas monossulfeniladas, efetuado com a finalidade de investigar a aplicabilidade sintética destes compostos. A obtenção de α-cetotioésteres é interpretada como uma reação de Pummerer não catalisada e se constitui em um método alternativo de preparação destes compostos. A decomposição térmica de sulfinil cetonas não sulfeniladas, efetuada para fins de comparação, mostrou-se mais complexa e de difícil interpretação. / The scope of this work consists of a study of reactions of carbanions of functionalyzed sulfoxides with sulfenylating reagents, employing two methods: in the homogeneous phase and by the phase transfer. The literature review, which is presented, shows that although these reactions are new, some other reactions of the carbanions of the functionalyzed sulfoxides, such as alkylations, acylations, condensations with carbonyl compounds and Michael addition, have been already reported. Furthermore, a small number of reactions of sulfinyl carbanions by phase transfer method has been described. The sulfenylation reaction, in the homogeneous phase of the α-sulfinyl aromatic (Ia-d) and cyclic (II) ketones, α-sulfinyl esters (IIIa,b) and thioesters (IVa,b) were performed employing NAH/DMSO and dimethyldissulfide or methyl methanethiosulfonate (MeSO2SMe). Except for the compound (IIb), which showed to be unreactive, in all other cases the monosulfenylated derivatives, not reported previously in the literature, were obtained. The yields of these compounds of 25-90% follow the order: Ib > Ia > IVa > Ic > Id > IIIa > II. The sulfenylation reactions by the phase transfer method were performed employing two different procedures: ion-pair extraction (A) and solid-liquid system (8). The procedure (A) was applied to the compounds Ia, IIIa and IVb, using NaOH/CH2Cl2/Bu4NHSO4 and MeS02SMe. While Ia and IIIa yielded the monosulfenylated derivatives in good yields, IVb remained unchanged. The sulfenylation reactions by procedure (B), using K2CO3/ΦH/TEBA and MeSO2SMe, carried out with the compounds Ia-d, IIIa and IVb, showed to be more satisfactory than by procedure (A), as all compounds afforded the monosulfenylated derivatives. The yield of compound IIIa was only of 20%, but those for other compounds were of 40-67%. The 1H-NMR analysis of the sulfenylated derivatives showed the presence of two diastereomers in equal quantities. It was possible, by replacement of TEBA by a quiral quininium salt, for the case of two sulfinyl ketones (Ia and Ic), to obtain the corresponding sulfenylated derivatives of diastereomeric ratio 4:1. This work presents also, having in application, the thermal decomposition monosulfenylated sulfinyl ketones. The mind the synthetic reaction of the obtention of the α-ketothioesters is interpreted as a non catalyzed Pummerer reaction and may be considered as an alternative method for preparation of these compounds. The thermal decomposition of the non-sulfenylated sulfinyl ketones performed for comparison, showed to be more complex and hardly to be interpreted.

A finalidade deste trabalho é o estudo de reações de carbânions de sulfóxidos funcionalizados com reagentes sulfenilantes, pelo emprego de dois métodos: fase homogênea e transferência de fases. A revisão bibliográfica apresentada demonstra que trata-se de reações novas e que, entretanto, outras reações de carbânions de sulfóxidos funcionalizados, tais como alquilações, acilações, condensações com compostos carbonílicos e adições de Michael, já tinham sido descritas. Por outro lado, poucas reações de sulfinil carbânions tinham sido efetuadas pelo emprego do método de transferência de fases. As reações de sulfenilação em fase homogênea de α-sulfinil cetonas aromáticas (Ia-d), e cíclicas (II), α-sulfinil ésteres (IIIa,b) e tioéster (IV) foram efetuadas pelo emprego de NaH/DMSO e de dimetildissulfeto ou metanotiossulfonato de metila (MeSO2SMe). Com exceção do composto (IIIb) que não reagiu, em todos os casos foram obtidos compostos monossulfenilados ainda não descritos na literatura. Os rendimentos variavam entre 25-90%, na ordem: Ib > Ia > IVa > Ic > Id > IIIa > II. As reações de sulfenilação em transferência de fases foram efetuadas pelo emprego de dois procedimentos distintos: o de extração do íon-par (A) e o sistema Sólido-líquido (B). Os compostos Ia, IIIa e IVb foram submetidos à sulfenilação pelo procedimento A, em que usou-se NaOH/CH2Cl2/Bu4NHSO4 e MeSO2SMe. Enquanto Ia e IIIa renderam produtos monossulfenilados em baixos rendimentos, IVb não reagiu. As reações de sulfenilação pelo procedimento B, usando-se K2CO3/ΦH/TEBA e MeSO2SMe foram efetuadas com os compostos Ia-d, IIIa e IVb e mostraram-se mais satisfatórias do que pelo procedimento A, pois todos reagiram, rendendo produtos monossulfenilados. O rendimento do composto IIIa era apenas de 20% , mas os rendimentos dos outros derivados variavam entre 40-67%. Observou-se, através da análise de RMN-1H, em todos os derivados sulfenilados, a presença de dois diastereoisômeros em quantidades iguais. Entretanto, substituindo-se o TEBA por um sal de quinínio quirálico, no caso de duas sulfinil cetonas (Ia e Ic) os compostos sulfenilados correspondentes mostraram uma relação diastereomérica de 4:1. O trabalho apresenta também os resultados de decomposição térmica de sulfinil cetonas monossulfeniladas, efetuado com a finalidade de investigar a aplicabilidade sintética destes compostos. A obtenção de α-cetotioésteres é interpretada como uma reação de Pummerer não catalisada e se constitui em um método alternativo de preparação destes compostos. A decomposição térmica de sulfinil cetonas não sulfeniladas, efetuada para fins de comparação, mostrou-se mais complexa e de difícil interpretação. / The scope of this work consists of a study of reactions of carbanions of functionalyzed sulfoxides with sulfenylating reagents, employing two methods: in the homogeneous phase and by the phase transfer. The literature review, which is presented, shows that although these reactions are new, some other reactions of the carbanions of the functionalyzed sulfoxides, such as alkylations, acylations, condensations with carbonyl compounds and Michael addition, have been already reported. Furthermore, a small number of reactions of sulfinyl carbanions by phase transfer method has been described. The sulfenylation reaction, in the homogeneous phase of the α-sulfinyl aromatic (Ia-d) and cyclic (II) ketones, α-sulfinyl esters (IIIa,b) and thioesters (IVa,b) were performed employing NAH/DMSO and dimethyldissulfide or methyl methanethiosulfonate (MeSO2SMe). Except for the compound (IIb), which showed to be unreactive, in all other cases the monosulfenylated derivatives, not reported previously in the literature, were obtained. The yields of these compounds of 25-90% follow the order: Ib > Ia > IVa > Ic > Id > IIIa > II. The sulfenylation reactions by the phase transfer method were performed employing two different procedures: ion-pair extraction (A) and solid-liquid system (8). The procedure (A) was applied to the compounds Ia, IIIa and IVb, using NaOH/CH2Cl2/Bu4NHSO4 and MeS02SMe. While Ia and IIIa yielded the monosulfenylated derivatives in good yields, IVb remained unchanged. The sulfenylation reactions by procedure (B), using K2CO3/ΦH/TEBA and MeSO2SMe, carried out with the compounds Ia-d, IIIa and IVb, showed to be more satisfactory than by procedure (A), as all compounds afforded the monosulfenylated derivatives. The yield of compound IIIa was only of 20%, but those for other compounds were of 40-67%. The 1H-NMR analysis of the sulfenylated derivatives showed the presence of two diastereomers in equal quantities. It was possible, by replacement of TEBA by a quiral quininium salt, for the case of two sulfinyl ketones (Ia and Ic), to obtain the corresponding sulfenylated derivatives of diastereomeric ratio 4:1. This work presents also, having in application, the thermal decomposition monosulfenylated sulfinyl ketones. The mind the synthetic reaction of the obtention of the α-ketothioesters is interpreted as a non catalyzed Pummerer reaction and may be considered as an alternative method for preparation of these compounds. The thermal decomposition of the non-sulfenylated sulfinyl ketones performed for comparison, showed to be more complex and hardly to be interpreted.

A presente Tese contém uma revisão bibliográfica sobre reações de Diels-Alder entre compostos carbonílicos e carboxílicos α,β-insaturados de cadeia aberta e ciclopentadieno. Várias reações novas são relatadas, tais como: 1). Oxidação de α-sulfenil tioésteres aos α-sulfinil tio ésteres correspondentes. 2). α-Alquilações de metilssulfinil-acetato de etila. 3). Reações de Pummerer de α-sulfinil tioésteres. 4). β-Eliminação de α-sulfinil tioésteres. 5). Reações de Diels-Alder dos tioésteres α,β-insaturados com ciclopentadieno, em ausência e em presença de catalisadores. Os resultados obtidos são discutidos e comparados com os descritos na literatura para reações com compostos semelhantes. Assim, nas reações de Pummerer, eles contribuíram para o esclarecimento dos mecanismos propostos. Nas reações de β-eliminação de α-sulfinil tioésteres, a estereoquímica mostrou-se concordante com a de α-sulfinil ésteres e α-sulfinil cetonas. Nas reações de Diels-Alder de tioésteres α,β-insaturados, foi observada uma estereosseletividade mais acentuada, tanto em ausência, como em presença de catalisadores, em comparação com os ésteres análogos. Foram isolados, identificados e caracterizados vinte e quatro compostos inéditos, entre os quais, cinco α-sulfenil tioésteres, seis α-sulfinil tioésteres, três α-sulfenil tioésteres α-substituídos, três tioésteres α,β-insaturados e sete tio ésteres norbornênicos. / This Thesis presents a literature review of the Diels-Alder reactions of open chained α,β-unsaturated carbonyl and carboxyl compounds with cyclopentadiene. Some new reactions are described, as follows: 1). Oxidation of α-sulfenyl-thioesters to the corresponding α-sulfinyl-thioesters. 2). α-Alkylations of ethyl methylsulfinylthioacetate. 3). Pummerer rearrangements of α-sulfinyl-thioesters. 4). (3-Eliminations of α-sulfinyl-thioesters. 5). Diels-Alder reactions of α,β-unsaturated thioesters with cyclopentadiene, in the absence and in the presence of catalysts. The results are discussed and compared with those described in the literature for reactions of the corresponding esters and ketones. In the case of the Pummerer reactions, the results contribute to the understanding of the mechanisms poroposed in the literature. In the β-elimination reactions of α-sulfinyl-thioesters, the stereochemistry showed to be in accordance with that for α-sulfinyl-esters and α-sulfinyl-ketones. In the Diels-Alder reactions of α,β-unsaturated thioesters, an enhanced stereoselectivity was observed, in comparison with the analogue esters, in the absence, as well as in the presence of catalysts. Twenty four new compounds were isolated, identified and characterized: eight α-sulfenyl-thioesters, six α-sulfinylthioesters, three α,β-unsaturated thioesters and seven norbornenic thioesters.

A presente Tese contém uma revisão bibliográfica sobre reações de Diels-Alder entre compostos carbonílicos e carboxílicos α,β-insaturados de cadeia aberta e ciclopentadieno. Várias reações novas são relatadas, tais como: 1). Oxidação de α-sulfenil tioésteres aos α-sulfinil tio ésteres correspondentes. 2). α-Alquilações de metilssulfinil-acetato de etila. 3). Reações de Pummerer de α-sulfinil tioésteres. 4). β-Eliminação de α-sulfinil tioésteres. 5). Reações de Diels-Alder dos tioésteres α,β-insaturados com ciclopentadieno, em ausência e em presença de catalisadores. Os resultados obtidos são discutidos e comparados com os descritos na literatura para reações com compostos semelhantes. Assim, nas reações de Pummerer, eles contribuíram para o esclarecimento dos mecanismos propostos. Nas reações de β-eliminação de α-sulfinil tioésteres, a estereoquímica mostrou-se concordante com a de α-sulfinil ésteres e α-sulfinil cetonas. Nas reações de Diels-Alder de tioésteres α,β-insaturados, foi observada uma estereosseletividade mais acentuada, tanto em ausência, como em presença de catalisadores, em comparação com os ésteres análogos. Foram isolados, identificados e caracterizados vinte e quatro compostos inéditos, entre os quais, cinco α-sulfenil tioésteres, seis α-sulfinil tioésteres, três α-sulfenil tioésteres α-substituídos, três tioésteres α,β-insaturados e sete tio ésteres norbornênicos. / This Thesis presents a literature review of the Diels-Alder reactions of open chained α,β-unsaturated carbonyl and carboxyl compounds with cyclopentadiene. Some new reactions are described, as follows: 1). Oxidation of α-sulfenyl-thioesters to the corresponding α-sulfinyl-thioesters. 2). α-Alkylations of ethyl methylsulfinylthioacetate. 3). Pummerer rearrangements of α-sulfinyl-thioesters. 4). (3-Eliminations of α-sulfinyl-thioesters. 5). Diels-Alder reactions of α,β-unsaturated thioesters with cyclopentadiene, in the absence and in the presence of catalysts. The results are discussed and compared with those described in the literature for reactions of the corresponding esters and ketones. In the case of the Pummerer reactions, the results contribute to the understanding of the mechanisms poroposed in the literature. In the β-elimination reactions of α-sulfinyl-thioesters, the stereochemistry showed to be in accordance with that for α-sulfinyl-esters and α-sulfinyl-ketones. In the Diels-Alder reactions of α,β-unsaturated thioesters, an enhanced stereoselectivity was observed, in comparison with the analogue esters, in the absence, as well as in the presence of catalysts. Twenty four new compounds were isolated, identified and characterized: eight α-sulfenyl-thioesters, six α-sulfinylthioesters, three α,β-unsaturated thioesters and seven norbornenic thioesters.