Non-enantioselective and enantioselective synthetic transformations using copper and iron salts for diazo insertion reactions into Si–H and S–H bonds and hydrosilylation reactions of ketones

Cette thèse décrit la découverte de transformations synthétiques énantiosélectives et non énantiosélectives dans lesquelles des catalyseurs chiraux et environnementalement bénins à base de cuivre, de fer et de zinc sont utilisés pour des réactions d’insertion de diazos dans les liaisons Si–H et S–H et pour des réactions d’hydrosilylation de cétones. Des réactions énantiosélectives et non énantiosélectives d’insertion de métal-carbènes d’α-diazoesters catalysées par le cuivre et le fer dans les liaisons Si–H et S–H sont décrites. Nous avons réussi à développer un protocole efficace pour la réaction d’insertion de métal-carbènes d’α-diazoesters catalysée par le cuivre et le fer dans les liaisons Si–H et S–H. Avec l’utilisation de [(MeCN)4Cu]PF6 et de Fe(OTf)2, une grande variété d’α-silylesters ont été synthétisés avec des bons et des excellents rendements (jusqu’à 98%). Ces catalyseurs peuvent aussi être utilisés efficacement pour l’insertion de métal-carbène dans la liaison S– H avec des bons rendements (jusqu’à 90%). Des résultats prometteurs ont été obtenus pour les réactions d’insertion de métal-carbènes d’α-diazoesters catalysées par le fer dans la liaison Si–H avec l’utilisation du DMC comme solvant vert en remplacement de CH2Cl2. Plusieurs ligands diamines chiraux ont été testés pour développer une réaction d’insertion de métal-carbène hautement énantiosélective dans la liaison Si–H avec l’utilisation du sel de cuivre peu coûteux [(MeCN)4Cu]PF6 comme catalyseur. Un excellent rendement ainsi qu’une excellente énantiosélectivité (rendement de 85%, 99:1 er) ont été obtenus lorsque les ligands contenant un coeur (R, R)-diaminocyclohexane et des groupements mésityles ont été utilisés. Il s’agit d’un très bon exemple de réaction hautement énantiosélective d’insertion dans la liaison Si–H avec l’utilisation d’aryldiazoacétates, de sources de silane peu coûteuses en comparaison avec d’autres et de ligands diamines chiraux facilement synthétisables ayant été utilisés pour la première fois dans la réaction d’insertion énantiosélective de métal-carbène dans la liaison Si–H. Nous avons découvert que les diamines chirales, facilement disponibles, sont aussi des ligands efficaces pour la réduction d’aryle-cétones avec le catalyseur Zn(OAc)2. Les alcools recherchés ont été obtenus avec des hauts rendements et de très bons rapports énantiomériques (rendements jusqu’à 99%, er jusqu’à 99:1). Nous avons aussi obtenu de bons résultats pour l’hydrosilylation de la pphényltrifluoroacetophénone avec l’utilisation d’un système bipybox-iPr/Fe(OAc)2...This thesis describes the development of non-enantioselective and enantioselective synthetic transformations using copper, iron, and zinc salts as environmentally benign catalysts for diazo insertion reactions into the Si–H and S–H bonds and hydrosilylation reactions of ketones. Non-enantioselective and enantioselective copper and iron-catalyzed metal carbene insertion reactions of α-diazoesters into Si–H and S–H bonds are described. We successfully developed an efficient copper and iron-catalyzed protocol for the metal carbene insertion reaction of α-diazoesters into Si–H and S–H bonds. By using [(MeCN)4Cu]PF6 and Fe(OTf)2, a wide range of α-silylesters were synthesized in good to excellent yields (up to 98%). These catalysts have been shown to be efficient for metal carbene insertion into S–H bond in high yields (up to 90%) as well. Excellet results have been obtained for iron-catalyzed carbene insertion reactions of α-diazoesters into Si–H bond using DMC as a green solvent instead of CH2Cl2. Several chiral diamine ligands were tested to develop a highly enantioselective metal carbene insertion reaction into the Si–H bond using the inexpensive copper salt [(MeCN)4Cu]PF6 as catalyst. Excellent yield and enantioselectivity (85% yield, 99:1 er) were obtained when the ligands containing a (R, R)- diaminocyclohexane core and mesityl groups were used. This is the very good example of highly enantioselective Si–H bond insertion reactions using aryldiazoacetates and inexpensive silane sources compare to others and easy-to-synthesize chiral diamine ligands that have been used for the first time for enantioselective Si–H bond insertion reaction. We have found that the readily available chiral diamines are also efficient ligands for the reduction of aryl ketones using Zn(OAc)2 as catalyst. The desired alcohols were obtained in high yields and very good enantiomeric ratios (up to 99% yields, up to 99:1 er). We also obtained good results for the hydrosilylation of p-phenyltrifluoroacetophenone using a bipybox-iPr/Fe(OAc)2 system (85% yield, 80:20 er). Based on the information in the literature, there are just a few examples on asymmetric hydrosilylation of pphenyltrifluoroacetophenone using ZnEt2 with very low enantioselectivities

Fe(OTf)2-catalyzed thia-Michael addition reaction : a green synthetic approach to β-thioethers

A convenient Fe(OTf)2‐catalyzed Michael addition reaction of thiols to α,β‐unsaturated carbonyl compounds was developed. The use of a simple procedure (EtOH, room temperature, air atmosphere) allowed to set up effective green catalytic conditions for the C‐S bond formation. The scope of the reaction was demonstrated using various substituted thiols and original Michael acceptors. The corresponding β‐thioethers were obtained in good to excellent yields (up to 99%). Also, the derivatization into the one‐pot thia‐Michael addition/oxidation reaction of 3‐(3‐(phenylthio)butanoyl)oxazolidin‐2‐one using H2O2 has proven to be efficient

New chiral bis(oxazolinyl)bipyridine ligands and application in the iron catalyzed asymmetric hydrosilylation of ketones

C2 symmetrical 6,6′-bis(oxazolinyl)-2,2′-bipyridine (bipybox) chiral ligands have been synthesized from readily available 2,2′-bipyridine. Catalytic asymmetric hydrosilylation of ketones was studied using this family of ligands in the presence of iron(II) acetate

Copper-catalyzed carbenoid insertion reactions of a-diazoesters and a-diazoketones into Si–H and S–H bonds

An efficient copper-catalyzed carbenoid insertion reaction of a-diazo carbonyl compounds into Si–H and S–H bonds was developed. A wide range of a-silylesters and a-thioesters was obtained in high yields (up to 98%) from a-diazoesters using 5 mol % of a simple copper(I) salt as catalyst. Using 0.05 mol % of the same catalyst, a-diazoketones led to a-silylketones in low to good yields (up to 70%)

Detection and Physical Interaction with Deformable Linear Objects

Deformable linear objects (e.g., cables, ropes, and threads) commonly appear in our everyday lives. However, perception of these objects and the study of physical interaction with them is still a growing area. There have already been successful methods to model and track deformable linear objects. However, the number of methods that can automatically extract the initial conditions in non-trivial situations for these methods has been limited, and they have been introduced to the community only recently. On the other hand, while physical interaction with these objects has been done with ground manipulators, there have not been any studies on physical interaction and manipulation of the deformable linear object with aerial robots. This workshop describes our recent work on detecting deformable linear objects, which uses the segmentation output of the existing methods to provide the initialization required by the tracking methods automatically. It works with crossings and can fill the gaps and occlusions in the segmentation and output the model desirable for physical interaction and simulation. Then we present our work on using the method for tasks such as routing and manipulation with the ground and aerial robots. We discuss our feasibility analysis on extending the physical interaction with these objects to aerial manipulation applications.Comment: Presented at ICRA 2022 2nd Workshop on Representing and Manipulating Deformable Objects (https://deformable-workshop.github.io/icra2022/

UAS Simulator for Modeling, Analysis and Control in Free Flight and Physical Interaction

This paper presents the ARCAD simulator for the rapid development of Unmanned Aerial Systems (UAS), including underactuated and fully-actuated multirotors, fixed-wing aircraft, and Vertical Take-Off and Landing (VTOL) hybrid vehicles. The simulator is designed to accelerate these aircraft's modeling and control design. It provides various analyses of the design and operation, such as wrench-set computation, controller response, and flight optimization. In addition to simulating free flight, it can simulate the physical interaction of the aircraft with its environment. The simulator is written in MATLAB to allow rapid prototyping and is capable of generating graphical visualization of the aircraft and the environment in addition to generating the desired plots. It has been used to develop several real-world multirotor and VTOL applications. The source code is available at https://github.com/keipour/aircraft-simulator-matlab.Comment: In proceedings of the 2023 AIAA SciTech Forum, Session: Air and Space Vehicle Dynamics, Systems, and Environments II

New chiral bis(oxazolinyl) bipyridine ligands and application in the iron catalyzed asymmetric hydrosilylation of ketones

C2 symmetrical 6,6'-bis(oxazolinyl)-2,2'-bipyridine (bipybox) chiral ligands have been synthesized from readily available 2,2'-bipyridine. Catalytic asymmetric hydrosilylation of ketones was studied using this family of ligands in the presence of iron(II) acetate

Demonstrating Large-Scale Package Manipulation via Learned Metrics of Pick Success

Automating warehouse operations can reduce logistics overhead costs, ultimately driving down the final price for consumers, increasing the speed of delivery, and enhancing the resiliency to workforce fluctuations. The past few years have seen increased interest in automating such repeated tasks but mostly in controlled settings. Tasks such as picking objects from unstructured, cluttered piles have only recently become robust enough for large-scale deployment with minimal human intervention. This paper demonstrates a large-scale package manipulation from unstructured piles in Amazon Robotics' Robot Induction (Robin) fleet, which utilizes a pick success predictor trained on real production data. Specifically, the system was trained on over 394K picks. It is used for singulating up to 5 million packages per day and has manipulated over 200 million packages during this paper's evaluation period. The developed learned pick quality measure ranks various pick alternatives in real-time and prioritizes the most promising ones for execution. The pick success predictor aims to estimate from prior experience the success probability of a desired pick by the deployed industrial robotic arms in cluttered scenes containing deformable and rigid objects with partially known properties. It is a shallow machine learning model, which allows us to evaluate which features are most important for the prediction. An online pick ranker leverages the learned success predictor to prioritize the most promising picks for the robotic arm, which are then assessed for collision avoidance. This learned ranking process is demonstrated to overcome the limitations and outperform the performance of manually engineered and heuristic alternatives. To the best of the authors' knowledge, this paper presents the first large-scale deployment of learned pick quality estimation methods in a real production system.Comment: Robotics: Science and Systems (RSS 2023) conference, July 10 - 14, 2023, Daegu, Republic of Kore

Pick Planning Strategies for Large-Scale Package Manipulation

Automating warehouse operations can reduce logistics overhead costs, ultimately driving down the final price for consumers, increasing the speed of delivery, and enhancing the resiliency to market fluctuations. This extended abstract showcases a large-scale package manipulation from unstructured piles in Amazon Robotics' Robot Induction (Robin) fleet, which is used for picking and singulating up to 6 million packages per day and so far has manipulated over 2 billion packages. It describes the various heuristic methods developed over time and their successor, which utilizes a pick success predictor trained on real production data. To the best of the authors' knowledge, this work is the first large-scale deployment of learned pick quality estimation methods in a real production system.Comment: 2023 IEEE/RSJ International Conference on Intelligent Robots and Systems (IROS), Learning Meets Model-based Methods for Manipulation and Grasping Worksho