Dihydrobiphenylenes through ruthenium-catalyzed [2+2+2] cycloadditions of ortho-alkenylarylacetylenes with alkynes.

A new synthetic route to dihydrobiphenylenes has been developed. The process involves a mild Ru(II) -catalyzed [2+2+2] dimerization of ortho-alkenylarylacetylenes or its more versatile variant, the Ru-catalyzed [2+2+2] cycloaddition of ortho-ethynylstyrenes with alkynes. Mechanistic aspects of this [2+2+2] cycloaddition are discussed.

Genetic similarities among four species of the Plectranthus ( L’Hér. ) genus / Similaridade genética de quatro espécies do gênero Plectranthus

The Plectranthus genus comprises several species generally referred to as boldo, which are highly used in popular medicine due to their anti-dyspeptic, analgesic and digestion-stimulating properties. The amount of natural active principles can vary greatly in the related genotypes, which may lead to the inappropriate use of these plants. This work aimed to analyze the interspecific diversity among four species of the Plectranthus genus (P. grandis, P. barbatus, P. neochilus and P. amboinicus) and the intraspecific diversity of P. barbatus collected from different places in southern Brazil, by means of the RAPD technique. A higher genetic similarity was observed between the P. neochilus and P. amboinicus species (80%), followed by P. grandis and P. barbatus (77%). P. barbatus genotypes from Passo Fundo and Porto Alegre showed a genetic similarity which was close to 100%, while the genetic similarity for P. barbatus genotypes from other locations was higher than 96%. Although a low variability among genotypes of this species was found in this study, RAPD markers allowed a clear differentiation among the analyzed genotypes, showing a 53% mean genetic similarity, with a high correlation value (r = 0.99), which proves a high agreement between the genetic similarity and clustering data.

O gênero Plectranthus abrange plantas de diversas espécies, referidas como boldo, que são utilizadas na medicina popular pelas suas propriedades antidispépticas, analgésicas e estimulantes da digestão. Genótipos relacionados podem diferir amplamente na quantidade de princípios ativos naturais, resultando no uso de plantas não-apropriadas à saúde da população. O objetivo do presente estudo foi avaliar a diversidade genética interespecífica de quatro espécies do gênero Plectranthus (P. grandis, P. barbatus, P. neochilus e P. amboinicus) e intraespecífica de P. barbatus, coletadas em diferentes localidades da região Sul do Brasil, por meio da técnica de RAPD (Random Amplified Polymorphic DNA). Foi observada maior similaridade genética entre as espécies P. neochilus e P. amboinicus (80%), seguido de P. grandis e P. barbatus (77%). Genótipos de P. barbatus provenientes de Passo Fundo e Porto Alegre apresentaram similaridade genética próximo a 100%, enquanto nas demais regiões foi superior a 96%. Embora no presente trabalho tenha sido detectada baixa variabilidade entre genótipos desta espécie, a técnica de RAPD permitiu clara separação entre as quatro espécies analisadas, apresentando uma similaridade genética média de 53%, com um valor de correlação alto (r = 0,99), demonstrando elevada representatividade dos dados de similaridade genética com os de agrupamento.

6Pi e- versus 8pi e- electrocyclization of 1-aryl- and heteroaryl-substituted (1Z,3Z)-1,3,5-hexatrienes: a matter of aromaticity.

Peri selectivity of the electrocyclization of 1-aryl- and heteroaryl-substituted (1Z,3Z)-1,3,5-hexatrienes, obtained by Ru-catalyzed linear coupling of 1,6-diynes to Z-propenyl(hetero)arenes, can be efficiently modulated depending on the aromaticity of the (hetero)arene: 1,3,5-hexatrienyl(hetero)arenes give 8pi e- electrocyclization with the exception of 1,3,5-hexatrienylbenzenes, which give 6pi e- electrocyclization.

Recent advances in "formal" ruthenium-catalyzed [2+2+2] cycloaddition reactions of diynes to alkenes.

"Formal" and standard RuII-catalyzed [2+2+2] cycloaddition of 1,6-diynes to alkenes gave bicyclic 1,3-cyclohexadienes in relatively good yields. When terminal 1,6-diynes 1 were used, two isomeric bicyclic 1,3-cyclohexadienes 4 or 6 were obtained, depending on the acyclic or cyclic nature of the alkene partner. When unsymmetrical substituted 1,6-diynes 7 were used, the reaction with acyclic alkenes took place regio- and stereoselectively to afford bicyclic 1,3-cyclohexadienes 8. A cascade process that behaves as a "formal" RuII-catalyzed [2+2+2] cycloaddition explained these results. Initially, a Ru-catalyzed linear coupling of 1,6-diynes 1 and 7 with acyclic alkenes occurs to give open 1,3,5-trienes of type 3, which after a thermal disrotatory 6e(-) pi-electrocyclization led to the final 1,3-cyclohexadienes 4 and 8. When disubstituted 1,6-diyne 10 was used with electron-deficient alkenes, new exo-methylene cyclohexadienes 12 arose from a competitive reaction pathway.

Formal and standard ruthenium-catalyzed [2 + 2 + 2] cycloaddition reaction of 1,6-diynes to alkenes: a mechanistic density functional study.

"Formal" and standard Ru(II)-catalyzed [2 + 2 + 2] cycloaddition of 1,6-diynes 1 to alkenes gave bicyclic 1,3-cyclohexadienes in relatively good yields. The neutral Ru(II) catalyst was formed in situ by mixing equimolecular amounts of [Cp*Ru(CH3CN)3]PF6 and Et4NCl. Two isomeric bicyclic 1,3-cyclohexadienes 3 and 8 were obtained depending on the cyclic or acyclic nature of the alkene partner. Mechanistic studies on the Ru catalytic cycle revealed a clue for this difference: (a) when acyclic alkenes were used, linear coupling of 1,6-diynes with alkenes was observed giving 1,3,5-trienes 6 as the only initial reaction products, which after a thermal disrotatory 6e-pi electrocyclization led to the final 1,3-cyclohexadienes 3 as probed by NMR studies. This cascade process behaved as a formal Ru-catalyzed [2 + 2 + 2] cycloaddition. (b) With cyclic alkenes, the standard Ru-catalyzed [2 + 2 + 2] cycloaddition occurred, giving the bicyclic 1,3-cyclohexadienes 8 as reaction products. A complete catalytic cycle for the formal and standard Ru-catalyzed [2 + 2 + 2] cycloaddition of acetylene and cyclic and acyclic alkenes with the Cp*RuCl fragment has been proposed and discussed based on DFT/B3LYP calculations. The most likely mechanism for these processes would involve the formation of ruthenacycloheptadiene intermediates XXIII or XXVII depending on the alkene nature. From these complexes, two alternatives could be envisioned: (a) a reductive elimination in the case of cyclic alkenes 7 and (b) a beta-elimination followed by reductive elimination to give 1,3,5-hexatrienes 6 in the case of acyclic alkenes. Final 6e-pi electrocyclization of 6 gave 1,3-cyclohexadienes 3.

Ru-catalyzed cyclization of terminal alkynals to cycloalkenes.

Cycloalkenes can be efficiently prepared by a new Ru-catalyzed cyclization of terminal alkynals. Under appropriate conditions, cycloisomerizations to conjugated aldehydes may be observed. Both processes involve catalytic Ru vinylidenes.

A new Ru-catalyzed cascade reaction forming polycyclic cyclohexadienes from 1,6-diynes and alkenes.

Functionalized bicyclic 1,3-cyclohexadienes can be easily prepared by a new cascade reaction which involves the Ru-catalyzed addition of acyclic alkenes to 1,6-diynes to give (Z)-hexatrienes, followed by a pure thermal 6e-pi electrocyclization.