Copper(I)-Catalyzed Intramolecular Hydroalkoxylation of Unactivated Alkenes

Abstract

A Cu(I)-Xantphos system catalyzed the intramolecular hydroalkoxylation of unactivated terminal alkenes, giving five- and six-membered ring ethers. This system is applicable to both primary and secondary alcohols. A reaction pathway involving the addition of the Cu-O bond across the C-C double bond is proposed. A chiral Cu(I) catalyst system based on the (R)-DTBM-SEGPHOS ligand promoted enantioselective reaction with moderate enantioselectivity.

Stereoselective Chemoenzymatic Synthesis of Optically Active Aryl-Substituted Oxygen-Containing Heterocycles

“…(R)-p-Chlorostyrene oxide could be prepared with the opposite configuration and in up to 96:4 er compared to baker's yeast, by subjecting to cyclization the α-chlorohydrin obtained from Lactobacillus reuteri DSM 20016. Since the wild-type whole-cell biocatalysts selected (baker's yeast and Lactobacillus reuteri DSM 20016) are cheap and commercially available, this methodology is auspicious for setting up industrially relevant and cost-effective biotransformations for a large-scale production of oxygen-containing heterocycles, and thus for the stereo-selective preparation of chiral drugs [18].…”

“…Asymmetric syntheses of optically active tetrahydrofurans have also been extensively investigated in the last few decades [16] because of their presence in many natural products and biologically active compounds (e.g., Goniothalesdiol, Figure 1). The preparation of chiral tetrahydrofurans has been efficiently performed by asymmetric cycloetherifications of hydroxy olefins in the presence of organocatalysts [17] or transition metals [18], or by the catalytic asymmetric hydrogenation of substituted furans [19]. Optically active halohydrins have been successfully employed for the preparation of several chiral non-racemic oxygenated heterocycles (e.g., epoxides, oxetanes, tetrahydrofurans, pyrans).…”

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.…”