In situ tether formation from amines and alcohols enabling highly selective Tsuji-Trost allylation and olefin functionalization

The use of tethers allows to overcome reactivity and selectivity issues often encountered with intermolecular reactions. Although tethers have been successfully applied for decades, their installation and removal usually requires additional steps. This minireview highlights the recent development of tethers that can be installed in situ on (homo)-allyl amines or alcohols for Tsuji-Trost allylation or double bond functionalization. In particular, the use of (hemi-)acetal tethers for highly regioselective and enantioselective Tsuji-Trost allylation was recently reported. Hydroamination of olefins starting from allylic amines could be achieved via a retro Cope-elimination using catalytic amount of an aldehyde for tether formation. Finally, bifunctionalizations of olefins were developed using either carbon dioxide or carbonyls/imines as tether precursors. These recent breakthroughs greatly enhanced the efficiency of the tethering approach for olefin functionalization, and will make it even more attractive for synthetic chemists in the future.

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Jérôme Waser, Ugo Jonathan Orcel
2017
Journal paper

Abstract

Official source

https://infoscience.epfl.ch/record/225861?ln=en

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Related concepts (3)

Amine

In chemistry, amines (əˈmi:n,_ˈæmi:n, ˈeɪmiːn) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group (these may respectively be called alkylamines and arylamines; amines in which both types of substituent are attached to one nitrogen atom may be called alkylarylamines). Important amines include amino acids, biogenic amines, trimethylamine, and aniline.

Carbon dioxide

Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature, and as the source of available carbon in the carbon cycle, atmospheric is the primary carbon source for life on Earth. In the air, carbon dioxide is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. Carbon dioxide is soluble in water and is found in groundwater, lakes, ice caps, and seawater.

Catalysis

Catalysis (kəˈtæləsɪs) is the process of change in rate of a chemical reaction by adding a substance known as a catalyst (ˈkætəlɪst). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quickly, very small amounts of catalyst often suffice; mixing, surface area, and temperature are important factors in reaction rate. Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction product, in the process of regenerating the catalyst.