Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles.

Title Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles.
Authors C.A. Malapit; D.R. Caldwell; I.K. Luvaga; J.T. Reeves; I. Volchkov; N.C. Gonnella; Z.S. Han; C.A. Busacca; A.R. Howell; C.H. Senanayake
Journal Angew Chem Int Ed Engl
DOI 10.1002/anie.201703471
Abstract

?-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of ?-ketonitriles. The products could be further derivatized to valuable chiral ?,?-disubstituted-?-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines.

Citation C.A. Malapit; D.R. Caldwell; I.K. Luvaga; J.T. Reeves; I. Volchkov; N.C. Gonnella; Z.S. Han; C.A. Busacca; A.R. Howell; C.H. Senanayake.Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles.. Angew Chem Int Ed Engl. 2017;56(24):69997002. doi:10.1002/anie.201703471

Related Elements

Boron

See more Boron products. Boron Bohr ModelBoron (atomic symbol: B, atomic number: 5) is a Block P, Group 13, Period 2 element with an atomic weight of 10.81. The number of electrons in each of boron's shells is 2, 3 and its electron configuration is [He] 2s2 2p1. The boron atom has a radius of 90 pm and a Van der Waals radius of 192 pm. Boron was discovered by Joseph Louis Gay-Lussac and Louis Jacques Thénard in 1808 and was first isolated by Humphry Davy later that year. Boron is classified as a metalloid is not found naturally on earth. Elemental BoronAlong with carbon and nitrogen, boron is one of the few elements in the periodic table known to form stable compounds featuring triple bonds. Boron has an energy band gap of 1.50 to 1.56 eV, which is higher than that of either silicon or germanium. The name Boron originates from a combination of carbon and the Arabic word buraqu meaning borax.

Rhodium

See more Rhodium products. Rhodium (atomic symbol: Rh, atomic number: 45) is a Block D, Group 9, Period 5 element with an atomic weight of 102.90550. Rhodium Bohr ModelThe number of electrons in each of Rhodium's shells is [2, 8, 18, 16, 1] and its electron configuration is [Kr] 4d8 5s1. The rhodium atom has a radius of 134 pm and a Van der Waals radius of 195 pm. Rhodium was discovered and first isolated by William Wollaston in 1804. In its elemental form, rhodium has a silvery white metallic appearance. Elemental RhodiumRhodium is a member of the platinum group of metals. It has a higher melting point than platinum, but a lower density. Rhodium is found in ores mixed with other metals such as palladium, silver, platinum, and gold. Rhodium is primarily used as the catalyst in the three-way catalytic converters of automobiles it is also highly valued in jewelry. The name Rhodium originates from the Greek word 'Rhodon,' which means rose.

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