Experimental and theoretical studies evidence an unconventional biradical character for the titanium enolates derived from α-alkoxy ketones and TiCl4. EPR experiments and ab initio calculations suggest that these titanium enolates have an open shell electronic ground state.
[reaction: see text] Highly stereoselective titanium-mediated aldol reactions based on lactate-derived ketones are reported. The stereochemical outcome of the process depends on the protecting group (PMB or Bn) and the Lewis acid (i-PrOTiCl(3) or TiCl(4)) used in the enolization step, the corresponding anti-syn or syn-syn aldols being prepared in high yields and with diastereomeric ratios up to 99:1.
Alternative titanium-mediated aldol procedures based on several protected beta-hydroxy ethyl ketones have been surveyed. Eventually, enolization of (S)-1-benzyloxy-2-methyl-3-pentanone (1) with (i-PrO)TiCl3/i-Pr2NEt provided a very reactive enolate that afforded the corresponding 2,4-syn-4,5-syn aldol adducts in high yields and diastereomeric ratios with a broad range of aldehydes.
Homeless individuals have a very high risk of TB infection and disease and contact investigation requires specific methods for them. Programmes of screening and supervised treatment should be ensured in this group.
[reaction: see text] Highly stereoselective approaches directed toward the synthesis of the C18-C27 fragment of superstolide A are disclosed taking ketone 6 and aldehyde 7 as the only sources of chirality.
Female pigs, fasted overnight, received an orthotopic liver transplant. During the nonhepatic phase, both blood glycerol and plasma free fatty acid concentrations increased, returning to basal values after the transplant, indicating that the liver is the main receptor of these products released in the blood from the glyceride breakdown in peripheral fat deposits. Blood glucose level rose during the nonhepatic phase, probably due in part to the perfusion of glucosated saline received by the animals during this phase. After liver transplant, blood glucose levels progressively decreased and this effect was greatly reduced by administering L-alanine. Our data indicate that metabolic changes in the donor's liver diminish the availability of gluconeogenetic substrates immediately following transplant, while administration of exogenous alanine permits faster restoration of gluconeogenetic function in the transplanted liver.
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