RESUMO
We report an asymmetric homocoupling of ortho-(iodo)arylphosphine oxides and ortho-(iodo)arylphosphonates resulting in highly enantioenriched axially chiral bisphosphine oxides and bisphosphonates. These products are readily converted to enantioenriched biaryl bisphosphines without need for chiral auxiliaries or optical resolution. This provides a practical route for the development of previously uninvestigated atroposelective biaryl bisphosphine ligands. The conditions have also proven effective for asymmetric dimerization of other, non-phosphorus-containing aryl halides.
Assuntos
Benzodioxóis/síntese química , Compostos de Bifenilo/síntese química , Complexos de Coordenação/química , Ácidos Fosforosos/síntese química , Catálise , Dimerização , Ligantes , Níquel/química , Oxazóis/química , Oxirredução , Piridinas/química , EstereoisomerismoRESUMO
A pyridinebis(oxazoline) cobalt complex is a very efficient precatalyst for the hydrosilylation of terminal alkynes with Ph2 SiH2 , providing α-vinylsilanes with high (Markovnikov) regioselectivity and broad functional-group tolerance. The vinylsilane products can be further converted into geminal borosilanes through Markovnikov hydroboration with pinacolborane and a bis(imino)pyridine cobalt catalyst.
RESUMO
We report the synthesis of cobalt complexes of novel iminopyridine-oxazoline (IPO) ligands and their application to the asymmetric hydroboration of 1,1-disubstituted aryl alkenes. The new catalysts afforded α-alkyl-ß-pinacolatoboranes with exclusive regioselectivity in high yields with up to 99.5% ee. Furthermore, we have applied this method to an efficient synthesis of naproxen.
RESUMO
An extremely efficient cobalt catalyst for the hydroboration of both vinylarenes and aliphatic α-olefins with pinacolborane is described, providing the anti-Markovnikov products with excellent regio- and chemoselectivity, broad functional-group tolerance, and high turnover numbers (up to 19,800). The alkene hydroboration route is further extended to a two-step, one-pot hydroboration and cross-coupling of alkylboronates with aryl chlorides.
RESUMO
A new series of estrogen-derived metal complexes were synthesized and characterized. The functionalized estrogen receptor ligands were prepared by a four-step synthetic strategy, and then three transition metal Pd, Ni, Zn were introduced readily to give the title metal complexes, in which the squaramide was introduced as ion acceptor for the first time in the development of estrogen-derived metal complexes for estrogen receptor. Upon binding to estrogen receptors, all of the estrogen conjugates exhibited acceptable binding affinity (up to 4.04% relative to estradiol), and in transcription assays, all the compounds are agonists on ERα. Molecular modeling studies suggest a structural basis for the agonist activity of these compounds.
Assuntos
Desenho de Fármacos , Estrogênios/química , Compostos Organometálicos/farmacologia , Receptores de Estrogênio/agonistas , Esteroides/química , Elementos de Transição/química , Relação Dose-Resposta a Droga , Humanos , Modelos Moleculares , Compostos Organometálicos/síntese química , Compostos Organometálicos/química , Relação Estrutura-AtividadeRESUMO
We disclose the synthesis of a series of manganese complexes of chiral iminopyridine oxazoline ligands and their application in the first manganese-catalyzed asymmetric ketone hydrosilylations. The most sterically hindered manganese catalyst bearing two CH(Ph)2 groups at the 2,6-ortho positions of the imino aryl ring and a tBu group on the oxazoline ring furnishes the secondary alcohols in high enantioselectivities and yields.
RESUMO
A series of iron complexes of chiral iminopyridine-oxazoline (IPO) ligands have been synthesized. The most sterically hindered iron catalyst exhibits excellent activity (up to 99% yield) and high enantioselectivity (up to 93% ee) in asymmetric hydrosilylation of aryl ketones.