Intramolecular Hydroalkoxylation of Unactivated Alkenes Using Silane–Iodine Catalytic System

Abstract

A novel catalytic system using I2 and PhSiH3 for the intramolecular hydroalkoxylation of unactivated alkenes is described. NMR study indicated that in situ generated PhSiH2I is a possible active catalytic species. This catalytic system allows an efficient intramolecular hydroalkoxylation of phenyl-, trialkyl-, and 1,1-dialkyl-substituted alkenes as well as a variety of unactivated monoalkyl- and 1,2-dialkyl-substituted alkenes at room temperature. Mechanistic consideration based on significant experimental observations is also discussed.

Transition metal-free direct dehydrogenative arylation of activated C(sp3)–H bonds: synthetic ambit and DFT reactivity predictions

“…For example, compound 3d could be rapidly converted to an unusually substituted carbazole ( 13 ) using PhMgBr, while the methyl ester functionality remained intact ( Scheme 10 , eqn (1)) 31 Additionally, compound 12a could be transformed, in two steps into a structurally complex tetrahydrofuran ( 15 ) which features an all carbon quaternary center ( Scheme 10 , eqn (2)). 32 …”

Bisphosphonium salt: an effective photocatalyst for the intramolecular hydroalkoxylation of olefins

“…Saturated cyclic ethers are important structural scaffolds found in many biologically active natural products, pharmaceuticals and agrochemicals [19]. One of the most straightforward and attractive synthetic strategies for constructing these cyclic ether motifs is the catalytic intramolecular hydroalkoxylation of alkenes enabled by transition metals or Lewis acids, generally delivering Markovnikov-type addition products [20,[21][22][23][24][25][26][27][28][29][30][31][32][33]. Recently, Nicewicz and coworkers reported a catalytic intramolecular anti-Markovnikov hydroalkoxylation of alkenes via visible light photoredox catalysis [34][35][36].…”

Platinum Single Atoms on Carbon Nanotubes as Efficient Catalyst for Hydroalkoxylation

“…Oxygen heterocyclic compounds have been much attention as important structural motif in a wide range of biological active molecules such as polyethers, antibiotics, marine macrocycles, and flavor compounds . Among many synthetic strategies, intramolecular addition of an OH bond (intramolecular hydroalkoxylation) is an atom‐economical, and therefore attractive approach for synthesis of saturated oxygen heterocycles . Until now, there have been many efforts to develop efficient catalysts such as brønsted acids, metal salts (Au, Ru, and Pt) and lanthanide complex to remove use of toxic metal ions …”

“…[1][2][3][4] Among many synthetic strategies, intramolecular addition of an O H bond (intramolecular hydroalkoxylation) is an atom-economical, and therefore attractive approach for synthesis of saturated oxygen heterocycles. 5,6 Until now, there have been many efforts to develop efficient catalysts such as brønsted acids, metal salts (Au, Ru, and Pt) and lanthanide complex to remove use of toxic metal ions. [7][8][9][10][11] Among them, in particular, the gold(I)-catalyzed intramolecular hydroalkoxylation has drawn extensive interest owing to the potential for both stereospecific and enantioselective transformations.…”