Synthesis of 1,3-Diols by O-Nucleophile Additions to Activated Alkenes

Abstract

The diastereoselective synthesis of 1,3-diols by addition of oxygen nucleophiles to activated alkenes is presented. This review focuses on homoallylic alcohol substrates that react with a relay compound to form an intermediate oxygen nucleophile, which in turn will lead to a protected 1,3-diol by intramolecular addition to the olefin moiety.1 Introduction2 Base Catalysis3 Organocatalysis4 Activation with Non-Metallic Electrophiles5 Activation with Transition Metal Derivatives6 Conclusions

Mechanochemistry and Eco-Bases for Sustainable Michael Addition Reactions

“…[ 2 , 3 ]. If intramolecular Michael additions are performed with sub-stoichiometric or catalytic bases in a homogenous medium [ 4 ], the bases are rarely recyclable [ 5 , 6 , 7 ].…”

Stereoselective Tandem Synthesis of syn-1,3-Diol Derivatives by Integrating Olefin Cross-Metathesis, Hemiacetalization, and Intramolecular Oxa-Michael Addition

“…Further investigations into the use of cationic Au­(I) complexes in our tandem reaction are currently underway. Importantly, these results demonstrated that, in contrast to previous relevant reactions, − our tandem reaction should be applicable to fragment assembly processes in complex polyol synthesis.…”

“…There has been a longstanding interest in developing efficient methods for stereocontrolled synthesis of 1,3-diol motifs because they are embedded in a plethora of biologically relevant polyketide natural products and pharmaceuticals. , Allylation and aldol reactions of carbonyl compounds are established synthetic methods for accessing 1,3-diol motifs within complex polyketides . Meanwhile, David A. Evans and Gauchet-Prunet have described that hemiacetalization/intramolecular oxa-Michael addition of δ-hydroxy α,β-unsaturated esters/amides with benzaldehyde in the presence of a catalytic amount of a strong base provides syn -1,3-dioxanes, which correspond to benzylidene acetal protected 1,3-diols . This reaction has been widely used in complex polyketide synthesis because of the synthetic versatility of the product syn -1,3-dioxanes .…”

Synthesis of 1,3‐Dioxan‐2‐ones by Photo‐Aerobic Selenium‐π‐Acid Multicatalysis

“…Carbonic acid esters play a critical role in numerous scientific disciplines such as material sciences (e.g., polycarbonates), [1] natural product research (Scheme 1A), [2] and synthetic methodology (Scheme 1B–D) [3] . With regard to the last category, cyclic carbonic acid esters such as 1,3‐dioxolan‐2‐ones and 1,3‐dioxan‐2‐ones have increasingly become a focal point of methodological efforts, since such motifs are frequently shown to serve as lynchpins for the stereoselective synthesis of 1,2‐ [4,5] and 1,3‐diols [6,7] . From a synthetic viewpoint, the olefinic double bond has emerged as a tactically privileged functional group for the construction of cyclic carbonic acid esters by – in part, stereocontrolled – intramolecular cyclizations of carbonate nucleophiles onto inherently or catalytically activated C−C π‐bonds [3,5] .…”