Oxidative Dehomologation of Aldehydes with Oxygen as a Terminal Oxidant

A mild, efficient protocol for oxidative cleavage of C-C bonds in aldehydes has been developed that employs alkali metal hydrides as reagents and oxygen from air as a terminal oxidant. The method is applicable to a broad substrate range. © 2017 American Chemical Society

УСПЕШНОЕ ХИРУРГИЧЕСКОЕ ЛЕЧЕНИЕ РАЗРЫВА АНЕВРИЗМЫ ВОСХОДЯЩЕГО ОТДЕЛА АОРТЫ С ТАМПОНАДОЙ СЕРДЦА У БОЛЬНОГО, ПРОЖИВАЮЩЕГО В ОТДАЛЕННОМ РАЙОНЕ

This is a description of a clinical case of a 30-year-old patient with rupture of ascending aorta aneurism due to vascular media degeneration. The rupture gap was associated with cardiac tamponade and shock. As the patient lived in an area remote from a cardiac surgery center, the situation was close to fatal. A team of doctors, which flew forth to the place of the patient’s residence, put a drainage into pericardial cavity which made transportation of the patient for surgery possible. Prostethic repair of ascending aorta with a valve-containing conduit was successful, but there were numerous complications during postoperative period. Longterm (1.5 year after) assessment of the patient showed good results.Представлено описание клинического случая пациента 30 лет с разрывом аневризмы восходящей аорты на фоне дегенерации медии. Разрыв сопровождался тампонадой сердца, шоком. Проживание в районе, отдаленном от кардиохирургического центра, делало ситуацию почти фатальной. Бригада врачей, вылетевших к месту проживания пациента, осуществила дренирование полости перикарда. После этого удалось перевезти больного к месту операции. Протезирование восходящей аорты клапаносодержащим кондуитом прошло успешно, но послеоперационный период протекал с множеством осложнений. Обследование пациента в отдаленном периоде (1,5 года) показало хороший результат

Oxidative Dehomologation of Aldehydes with Oxygen as a Terminal Oxidant

A mild, efficient protocol for oxidative cleavage of C-C bonds in aldehydes has been developed that employs alkali metal hydrides as reagents and oxygen from air as a terminal oxidant. The method is applicable to a broad substrate range. © 2017 American Chemical Society

Oxidative azo-ene cyclization

An expedient procedure for catalytic oxidative azo-ene cyclization of allylic and homoallylic 1,2-hydrazinedicarboxylates is reported. The reaction produced a wide range of cyclic carbamate derivatives featuring an appended alkene fragment ready for further functionalization. © 2016 American Chemical Society

The complexity of planar Boolean #CSP with complex weights

A synthesis of new bidentate pyridines 8a-d, 9, and 10 has been developed, starting from triflate 14, readily available from beta-pinene 11. A copper complex of the pyridine-oxazoline ligands 8a has been found to catalyze asymmetric allylic oxidation of cyclic olefins 36a-c with good conversion rates and acceptable enantioselectivity (<= 67% ee). The imidazolium salt 10 has been identified as a precursor of the corresponding N,N'-unsymmetrical N-heterocyclic carbene ligand, whose complex with palladium catalyzed the intramolecular amide enolate alpha-arylation leading to oxindole 45 in excellent yield but with low enantioselectivity.

Oxidative azo-ene cyclization

An expedient procedure for catalytic oxidative azo-ene cyclization of allylic and homoallylic 1,2-hydrazinedicarboxylates is reported. The reaction produced a wide range of cyclic carbamate derivatives featuring an appended alkene fragment ready for further functionalization. © 2016 American Chemical Society

Dynamic kinetic resolution in the asymmetric synthesis of beta-amino acids by organocatalytic reduction of enamines with trichlorosilane

A new methodology based on the organocatalytic asymmetric hydrosilylation of enamines that allows a direct access to a range of β and β -amino acid derivatives was presented. The results show a successful reduction of aromatic substrates, a sterically more hindered ortho-substituted derivatives, and the thiophenyl analogue exhibiting lower reactivity. Fast enamine-imine equilibration is crucial as imines are chiral but racemic, while α-alkyl β-amino acids can be accessed by the symmetrical Mannich reaction. The α-alkyl derivatives have relative and absolute configuration due to their reduction with LiAlH into a known amino alcohols. Predominant formation of the anti isomer in 3o is consistent with conformation of the imine intermediate in the catalytic reduction