A Novel Type of Dyotropic Rearrangement. Palladium-Catalyzed Rearrangement of Alkoxymethyl-Substituted Silanes to Alkyl Silyl Ethers

Abstract

The treatment of alkoxymethyl-substituted hydrosilanes with palladium on charcoal gave rise to the corresponding alkyl silyl ethers by the migration of the silicon-bound hydrogen atom to the -carbon atom and of the alkoxy group to the silicon center. Kinetic investigations revealed that two parallel reactions are involved in the rearrangement: an intramolecular reaction, following pseudo-first-order kinetics and showing an inverse kinetic deuterium isotope effect, is dominant in the initial phase of the transformation, and an intermolecular reaction becomes important in the later course of the transformation. The dominant reaction in the first phase of the transformation has to be classified as a dyotropic arrangement of type I, due to the intramolecular course and the reaction order, and it represents the first catalyzed example of a rearrangement of this type.

Versatile Dehydrogenative Alcohol Silylation Catalyzed by Cu(I)—Phosphine Complex.

“…H NMR (300 MHz, CDCl 3 , d): 0.61 (q, J = 8.0 Hz, 6H, -SiCH 2 CH 3 ), 0.97 (t, J = 7.8 Hz, 9H, SiCH 2 CH 3 ), 1.11 (t, J = 7.5 Hz, 3H, -CH 2 CH 3 ), 2.16 (tq, J = 2.2, 7.5 Hz, 2H, CH 3 CH 2 CC-), 2.38 (tt, J NMR spectral data were in agreement with those in the literature 8. …”

Type-I dyotropic rearrangement for 1,2-disubstituted cyclohexanes: substitution effect on activation energy

“…3 Contrary to this, type-II dyotropic rearrangement 4 occurs via migration of two substituents to new sites in a molecule. In addition to a usual C-C 5 stationary scaffold, dyotropic reaction has been successfully applied to C-B, 6 C-N, 7 C-O, 8 C-Al, 9 C-Si, 10 C-S, 8,11 C-Cu, 12 C-Zn, 13 C-Zr, 14 C-Pd, 15 C]Si, 16 N-N, 17 O-N, 18 Si]Si, 19 Fe-Pt, 20 and Ge]Sn, 21 used as static frameworks. This double migration approach has been articulately incorporated to construct structurally complex molecules of synthetic and biological relevance such as lacrimin A (1), 22 jaspamide (2), 23 zoapatanol (3), 24 and azafenestrane (4, Fig.…”

Synthesis of a phosphine imide bearing a hydrosilane moiety, and its water-driven reduction to a phosphine

“…Synthesis of a phosphine imide bearing a hydrosilane moiety, and its water-driven reduction to a phosphine † ‡ Hydrosilanes, R 3 Si-H, are useful for hydrosilylation of multiple bonds, 1 reduction of various functional groups, 2 reductive aldol reactions, 3 and preparation of a silanol, R 3 Si-OH, by hydrolysis. 4 In some hydrosilanes, the silicon-bound hydrogen migrates intramolecularly through the 1,2-shift of the dyotropic rearrangement, 5 1,3-shift, 6 and 1, 5-shift. 7 As represented by the 1,3-hydride shift, the hypercoordinated hydrosilanes show hydride reducing reactivity without catalysis.…”