Synthesis of Alkynylmethylidene-benzoxasiloles through a Rhodium-Catalyzed Cycloisomerization Involving 1,2-Silicon and 1,3-Carbon Migration.

Title Synthesis of Alkynylmethylidene-benzoxasiloles through a Rhodium-Catalyzed Cycloisomerization Involving 1,2-Silicon and 1,3-Carbon Migration.
Authors T. Namba; S. Kawauchi; Y. Shibata; H. Kanno; K. Tanaka
Journal Angew Chem Int Ed Engl
DOI 10.1002/anie.201612560
Abstract

It is shown that a cationic rhodium(I)/biphep complex catalyzes the cycloisomerization of 2-(alkynylsilylethynyl)phenols, leading to alkynylmethylidene-benzoxasiloles through concomitant silicon and carbon migration. This unprecedented cycloisomerization presumably proceeds via the formation of rhodium vinylidenes through 1,2-silicon migration, followed by 1,3-carbon (alkyne) migration via the formation of hypervalent silicon centers.

Citation T. Namba; S. Kawauchi; Y. Shibata; H. Kanno; K. Tanaka.Synthesis of Alkynylmethylidene-benzoxasiloles through a Rhodium-Catalyzed Cycloisomerization Involving 1,2-Silicon and 1,3-Carbon Migration.. Angew Chem Int Ed Engl. 2017. doi:10.1002/anie.201612560

Related Elements

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.

Silicon

See more Silicon products. Silicon (atomic symbol: Si, atomic number: 14) is a Block P, Group 14, Period 3 element with an atomic weight of 28.085. Silicon Bohr MoleculeThe number of electrons in each of Silicon's shells is 2, 8, 4 and its electron configuration is [Ne] 3s2 3p2. The silicon atom has a radius of 111 pm and a Van der Waals radius of 210 pm. Silicon was discovered and first isolated by Jöns Jacob Berzelius in 1823. Silicon makes up 25.7% of the earth's crust, by weight, and is the second most abundant element, exceeded only by oxygen. The metalloid is rarely found in pure crystal form and is usually produced from the iron-silicon alloy ferrosilicon. Elemental SiliconSilica (or silicon dioxide), as sand, is a principal ingredient of glass, one of the most inexpensive of materials with excellent mechanical, optical, thermal, and electrical properties. Ultra high purity silicon can be doped with boron, gallium, phosphorus, or arsenic to produce silicon for use in transistors, solar cells, rectifiers, and other solid-state devices which are used extensively in the electronics industry.The name Silicon originates from the Latin word silex which means flint or hard stone.

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