Catalytic Asymmetric Hydroalkoxylation of C–C Multiple Bonds

Abstract

Asymmetric hydroalkoxylation of alkenes constitutes a redox-neutral and 100% atom-economical strategy toward enantioenriched oxygenated building blocks from readily available starting materials. Despite their great potential, catalytic enantioselective additions of alcohols across a C–C multiple bond are particularly underdeveloped, especially compared to other hydrofunctionalization methods such as hydroamination. However, driven by some recent innovations, e.g., asymmetric MHAT methods, asymmetric photocatalytic methods, and the development of extremely strong chiral Brønsted acids, there has been a gratifying surge of reports in this burgeoning field. The goal of this review is to survey the growing landscape of asymmetric hydroalkoxylation by highlighting exciting new advances, deconstructing mechanistic underpinnings, and drawing insight from related asymmetric hydroacyloxylation and hydration. A deep appreciation of the underlying principles informs an understanding of the various selectivity parameters and activation modes in the realm of asymmetric alkene hydrofunctionalization while simultaneously evoking the outstanding challenges to the field moving forward. Overall, we aim to lay a foundation for cross-fertilization among various catalytic fields and spur further innovation in asymmetric hydroalkoxylations of C–C multiple bonds.

Recent advances in electrooxidative radical transformations of alkynes

“…Alkynes are of major importance in various compounds of relevance to inter alia material sciences and chemical biology, while frequently being used as key intermediates in molecular syntheses [1][2][3][4][5][6][7][8][9][10]. The direct difunctionalization of alkynes represents an attractive approach for syntheses of multi-substituted alkenes, themselves representing important structural skeletons frequently found in natural products and biologically active molecules [11][12][13].…”

Three New Difunctional Electrocatalysts Built from Polyoxometalates and Cu–Tpy Units: Experimental and Theoretical Study

“…In this work, we chose copper ions to build Cu–organic complexes because it has adjustable coordination numbers and strong coordination ability to O and N atoms from carboxylic acids and nitrogenous ligands. Furthermore, it possesses a wide range of applications in electrodes, catalysts, − alloy nanocrystals, composite materials, , and biochemistry . For example, copper­(I)-catalyzed alkyene–azide cycloaddition reactions in glycoscience had been reported by Hotha et al in chemical reviews; the CO 2 photoreduction reaction has been adjusted by a highly selective Cu/X (X = Cl or adenine) catalyst because of hydrogen bond synergy for both Cu–X and CO 2 derivatives .…”

Pyrimidopteridine‐catalyzed Photo‐mediated Hydroacetoxylation

“…Carboxylic acids are attractive starting materials for hydrofunctionalization reactions. [5], [6] Organic photoredox catalysts have been particularly widely used in this context. [7] Photomediated CÀ O bond formations with carboxylic acids catalyzed by acridinium Photoredox catalysts and a HAT co-catalyst have previously been reported by the groups of Lei and Nicewicz.…”