Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis.

Title Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis.
Authors X. Jiang; P. Boehm; J.F. Hartwig
Journal J Am Chem Soc
DOI 10.1021/jacs.7b12824
Abstract

We report stereodivergent allylic substitution reactions of allylic esters with prochiral enolates derived from azaaryl acetamides and acetates to form products from addition of the enolates at the most substituted carbon of an allyl moiety with two catalysts, a chiral metallacyclic iridium complex and a chiral bisphosphine-ligated copper(I) complex, which indi-vidually control the configuration of the electrophilic and nucleophilic carbon atoms, respectively. By simple permuta-tions of enantiomers of the two catalysts, all four stereoiso-mers of products containing two stereogenic centers were syn-thesized individually with high diastereoselectivity and enan-tioselectivity. A variety of azaaryl acetamides and acetates bearing pyridyl, benzothiazolyl, benzoxazolyl, pyrazinyl, quinolinyl and isoquinolinyl moieties were all found to be suitable for this transformation.

Citation X. Jiang; P. Boehm; J.F. Hartwig.Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis.. J Am Chem Soc. 2018. doi:10.1021/jacs.7b12824

Related Elements

Iridium

See more Iridium products. Iridium (atomic symbol: Ir, atomic number: 77) is a Block D, Group 9, Period 6 element with an atomic weight of 192.217. The number of electrons in each of iridium's shells is [2, 8, 18, 32, 15, 2] and its electron configuration is [Xe] 4f14 5d7 6s2. Iridium Bohr ModelThe iridium atom has a radius of 136 pm and a Van der Waals radius of 202 pm. Iridium was discovered and first isolated by Smithson Tennant in 1803. In its elemental form, Iridium has a silvery white appearance. Iridium is a member of the platinum group of metals.Elemental Iridium It is the most corrosion resistant metal known and is the second-densest element (after osmium). It will not react with any acid and can only be attacked by certain molten salts, such as molten sodium chloride. Iridium is found as an uncombined element and in iridium-osmium alloys. Iridium's name is derived from the Greek goddess Iris, personification of the rainbow, on account of the striking and diverse colors of its salts.

Copper

See more Copper products. Copper Bohr Model Copper (atomic symbol: Cu, atomic number: 29) is a Block D, Group 11, Period 4 element with an atomic weight of 63.546. The number of electrons in each of copper's shells is 2, 8, 18, 1 and its electron configuration is [Ar]3d10 4s1. The copper atom has a radius of 128 pm and a Van der Waals radius of 186 pm. Copper was first discovered by Early Man prior to 9000 BC. In its elemental form, copper has a reddish-orange metallic and lustrous appearance. Of all pure metals, only silver Elemental Copperhas a higher electrical conductivity. The origin of the word copper comes from the Latin word 'cuprium' which translates as "metal of Cyprus," as the Mediterranean island of Cyprus was known as an ancient source of mined copper..

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