Iron-mediated Preparation of Vinylcyclopropanes. Scope, Mechanism, and Applications

The addition of stabilized carbon nucleophiles to tricarbonyl(1-methoxycarbonylpentadienyl)iron(1+) cation (1a) proceeds via attack at C2 on the face of the ligand opposite the Fe(CO)3 group to generate tricarbonyl(pentenediyl)iron complexes 2. Oxidation of complexes 2 affords vinylcyclopropanecarboxylates in good yield. In general, the relative stereochemistry about the cyclopropane ring reflects reductive elimination with retention of configuration. In cases where the C2 substituent is bulky (i.e., 2b) the major cyclopropane product 9b represents ring closure with inversion at C3. A mechanism involving π−σ−π rearrangement of the initially oxidized (pentenediyl)iron species is proposed to account for these results. Experiments which probe the stereochemistry of deuterium labeling in the vinyl group of the vinylcyclopropanecarboxylate products were carried out, and these results are consistent with the proposed mechanism. This methodology for the preparation of vinylcyclopropanecarboxylates was applied to the synthesis of 2-(2‘-carboxycyclopropyl)glycines (+)-22 and (−)-23 and the cyclopropane triester (−)-26

Enantioselective synthesis of the C11–C17 segment of soraphen A1α via organoiron methodology

The C11–C17 segment of the antifungal agent soraphen A1α was prepared from glyceraldehyde acetonide in nine steps. The C12 stereocenter is derived from glyceraldehyde, while the C17 stereocenter as introduced by 1,6-asymmetric control via the coordinated Fe(CO)3. The C11–C17 segment of the antifungal agent soraphen A1α, with required inverted stereochemistry at C17, was prepared. The C12 stereocenter is derived from glyceraldehyde, while the C17 stereocenter is introduced by 1,6-asymmetric induction via a coordinated Fe(CO)3

Development of Organoiron Methodology for the C8-C16 Dienylamine Segment of the Streptogramin Antibiotics

Methodology for preparation of the C8-C16 dienylamine segment of the streptogramin antibiotics is based on a diastereoselective nitrile oxide-olefin cycloaddition to a (triene)iron complex. The Fe(CO)3 adjunct also serves as a protecting group for the subsequent reductive hydrolysis of the isoxazoline ring

Image Human Thorax Using Ultrasound Traveltime Tomography with Supervised Descent Method

The change of acoustic velocity in the human thorax reflects the functional status of the respiratory system. Imaging the thorax’s acoustic velocity distribution can be used to monitor the respiratory system. In this paper, the feasibility of imaging the human thorax using ultrasound traveltime tomography with a supervised descent method (SDM) is studied. The forward modeling is computed using the shortest path ray tracing (SPR) method. The training model is composed of homogeneous acoustic velocity background and a high-velocity rectangular block moving in the domain of interest (DoI). The average descent direction is learned from the training set. Numerical experiments are conducted to verify the method’s feasibility. Normal thorax model experiment proves that SDM traveltime tomography can efficiently reconstruct thorax acoustic velocity distribution. Numerical experiments based on synthetic thorax model of pleural effusion and pneumothorax show that SDM traveltime tomography has good generalization ability and can detect the change of acoustic velocity in human thorax. This method might be helpful for the diagnosis and evaluation of respiratory diseases

Image Human Thorax Using Ultrasound Traveltime Tomography with Supervised Descent Method

The change of acoustic velocity in the human thorax reflects the functional status of the respiratory system. Imaging the thorax’s acoustic velocity distribution can be used to monitor the respiratory system. In this paper, the feasibility of imaging the human thorax using ultrasound traveltime tomography with a supervised descent method (SDM) is studied. The forward modeling is computed using the shortest path ray tracing (SPR) method. The training model is composed of homogeneous acoustic velocity background and a high-velocity rectangular block moving in the domain of interest (DoI). The average descent direction is learned from the training set. Numerical experiments are conducted to verify the method’s feasibility. Normal thorax model experiment proves that SDM traveltime tomography can efficiently reconstruct thorax acoustic velocity distribution. Numerical experiments based on synthetic thorax model of pleural effusion and pneumothorax show that SDM traveltime tomography has good generalization ability and can detect the change of acoustic velocity in human thorax. This method might be helpful for the diagnosis and evaluation of respiratory diseases