Highly Strained Tertiary sp³ Scaffolds: Synthesis of Functionalized Cubanes and Exploration of Their Reactivity under Pd(II) Catalysis

A series of chemically distinct, highly strained, activated cubane scaffolds were synthesized through optimization of the metal–halogen exchange reactions of iodinated cubane derivatives. This included the first reported successful attachment of both boron and phosphorus, key elements in potential transition-metal-catalyzed cross-coupling reactions, on the cubane scaffold. Additionally, Zn, Sn, Si, S, and various C-based systems were also attached in a high-yielding, one-pot reaction from readily available precursors. A comprehensive program investigating the reactivity of these tertiary cubane nucleophiles toward Suzuki–Miyaura, Negishi, and Stille cross-coupling methods, never previously reported with the cubane scaffold, is also described, but proved unsuccessful

Synthesis of a Family of Highly Substituted Porphyrin Thioethers via Nitro Displacement in 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetranitroporphyrin

A series of highly substituted porphyrin thioethers was synthesized from 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetranitroporphyrin (H₂OETNP). The reactions proceeded via a S_NAr mechanism with a broad range of aromatic thiols in the presence of a base. This is a rapid way to prepare a large variety of meso-substituted porphyrins from only one precursor. Single crystal X-ray analysis revealed that these new porphyrin thioethers are highly distorted, exhibiting conformational properties that are distinctive of both meso-sulfur substitution and steric overcrowding in general. Additionally, denitration of H₂OETNP under basic conditions was investigated, yielding products of stepwise desubstitution. This allowed a comparative X-ray crystallographic study to delineate the successive structural effects of an increasing degree of nitro substitution in the complete series of nitro-substituted octaethylporphyrins

Estudo cefalométrico comparativo dos espaços naso e bucofaríngeo nas más oclusões Classe I e Classe II, Divisão 1, sem tratamento ortodôntico, com diferentes padrões de crescimento A Comparative cephalometric study of the naso and oropharyngeal space in malocclusions Class I and Class II Division 1, without orthodontic treatment with different growth patterns

A finalidade deste estudo foi comparar os espaços aéreos naso e bucofaríngeo em indivíduos com má oclusão Classe I e Classe II, divisão 1, segundo Angle, do gênero masculino e feminino, com idade média de 11 anos e 6 meses, com padrão de crescimento normal e vertical, não tratados ortodonticamente. A amostra desse estudo foi dividida em dois grupos: 40 pacientes apresentando Classe I e 40 pacientes com Classe II, divisão 1, cada grupo subdividido de acordo com o padrão de crescimento facial: normal e vertical. Os espaços aéreos naso e bucofaríngeo foram avaliados segundo a análise de McNamara Jr., pelas medidas NFa-NFp e BFa-BFp. A análise dos resultados obtidos revelou que, a medida do espaço bucofaríngeo para Classe I com padrão de crescimento vertical e para o espaço nasofaríngeo para Classe II com padrão normal de crescimento apresentaram-se semelhantes à medida padrão da amostra de McNamara Jr.. As outras medidas apresentaram-se estatisticamente menores. Na comparação entre os grupos, o espaço nasofaríngeo no grupo Classe I com padrão de crescimento vertical, apresentou-se menor do que nos grupos Classe I e grupo Classe II divisão 1, ambos com padrão de crescimento normal. O espaço bucofaríngeo não sofreu alteração significante de um grupo para outro. Em relação à hipertrofia da tonsila faringeana, apenas o grupo Classe I com padrão de crescimento vertical apresentou obstrução; para hipertrofia das tonsilas palatinas, apenas o grupo Classe I com padrão de crescimento vertical e Classe II com padrão de crescimento normal apresentou hipertrofia das tonsilas palatinas.<br>The aim of this study is to compare the naso and oropharyngeal air space in people with malocclusion class I and class II division 1, according to Angle, with mean age from 8 to 15 years old with normal and vertical growth pattern not treated orthodontically. This study was divided into two groups: 40 patients with class I, and 40 with class II, division 1 subdivided according to facial growth: normal and vertical. The naso and oropharyngeal airway space was assessed according to McNamara's analysis by using the Nfa-NFp and Nba-NBp measurements. The analysis of the results obtained revealed that, the oropharyngeal measurements for class I with pattern vertical growth and nasopharyngeal class II with pattern normal growth were similar to the reference measures in McNamara's sample. The other measurements were statistically smaller. In the comparison between groups, the oropharyngeal spaces did not show a difference between one group and another. The nasopharyngeal space in the class I group with vertical growth, showed a narrower space than in the class I group and in the class II group with pattern normal growth. In relation to adenoids hypertrophy, only class I with pattern vertical growth showed obstruction; for tonsils hypertrophy, only class I with pattern vertical growth and class II with pattern normal growth showed tonsils hypertrophy