Arynic Condensation of Ketone Enolates XX. New Access To Polycyclic Phenylethanolamines

A new preparation of two kinds of potentially biologically active phenylethanolamines is described. The basic reaction of these syntheses is arynic condensation of ketone enolates in the presence of Complex Bases.     

The Allylic Alkylation of Ketone Enolates

The palladium-catalyzed allylic alkylation of non-stabilized ketone enolates was thought for a long time to be not as efficient as the analogous reactions of stabilized enolates, e. g. of malonates and β-ketoesters. The field has experienced a rapid development during the last two decades, with a range of new, highly efficient protocols evolved. In this review, the early developments as well as current methods and applications of palladium-catalyzed ketone enolate allylations will be discussed.     

Enantioselective Protonation of Enolates and Enols

Enantioselective protonation, until recently a largely overlooked reaction, has, in the last five years, developed into a field of intense research activity. The progress achieved parallels or complements that obtained in the understanding of enolate structures and reactivities. The conceptual simplicity and attractiveness of enantioselective protonation results from the fact that after reaction, the chiral proton donor is regenerated in its original protonated form by an extractive workup. Enantioselective protonation has been applied to the synthesis of amino acids, antiinflammatory agents (2-arylpropanoic acids), and fragrance compounds such as (S)-α-damascone, for which its industrial feasibility has been demonstrated.     

Enolonium Species—Umpoled Enolates

Enolonium species/iodo(III)enolates of carbonyl compounds have been suggested to be intermediates in a wide variety of hypervalent iodine induced chemical transformations of ketones, including α‐C−O, α‐C−N, α‐C−C, and α‐carbon–halide bond formation, but they have never been characterized. We report that these elusive umpoled enolates may be made as discrete species that are stable for several minutes at −78 °C, and report the first spectroscopic identification of such species. It is shown that enolonium species are direct intermediates in C−O, C−N, C−Cl, and C−C bond forming reactions. Our results open up chemical space for designing a variety of new transformations. We showcase the ability of enolonium species to react with prenyl, crotyl, cinnamyl, and allyl silanes with absolute regioselectivity in up to 92 % yield.     

一种测定六价铬的新方法

基于六价铬在稀盐酸介质中氧化盐酸羟胺产生亚硝酸根 ,而亚硝酸根可使对硝基苯胺重氮化并与α -萘胺偶联产生红色偶氮染料 ,提出了分光光度法测定六价铬的新方法。在最佳实验条件下 ,六价铬的浓度在0～ 5 0 μg/2 5mL内服从比耳定律 ,其线性相关系数γ为 0 .9990 ,表观摩尔吸光度ε51 0 为 2 .48× 1 0 4 L·mol- 1 ·cm- 1 。所拟方法用于水样中微量铬的测定 ,结果满意     

C-Acylation of Tertiary Enolates via Dithioesters

The acylation of unsymmetrical ketones to β-ketoesters at a tertiary enolate center can be selectively achieved by way of the stable β-dithioketoesters (eg, 2). These undergo one-step or sequential conversion to the β-ketoesters using Hg0-BF₃.     

Formylation of O-Silylated Enolates by Vilsmeier's Reagent

Reaction of trimethylsilylenol ethers and Vilsmeier's reagent leads to the corresponding regiocontrolled β-dicarbonyl compounds with high to good yields.     

Stereoselective Formation of Fully Substituted Ketone Enolates

The application of stereochemically defined acyclic fully substituted enolates of ketones to the enantioselective synthesis of quaternary carbon stereocenters would be highly valuable. Herein, we describe an approach leading to the formation of several new stereogenic centers through a combined metalation–addition of a carbonyl–carbamoyl transfer to reveal in situ stereodefined α,α‐disubstituted enolates of ketone as a single stereoisomer. This approach could produce a series of aldol and Mannich products from enol carbamate with excellent diastereomeric ratios.     

Reactions of Methylphenylvinylsulfonium Tetrafluoroborate with Ketone Enolates

The reactions of methylphenylvinylsulfonium tetrafluoroborate (1) with the lithium enolates of 1,3-dicarbonyl compounds, acyclic ketones and cyclic ketones have been studied. Cyclopropanes and cyclic ethers are obtained. The reaction mechanisms are also discussed.     

Effects of Anchimeric Assistance in Phosphonium Enolates Chemistry

Russian Journal of General Chemistry - Phosphonium enolates are key intermediates of phosphine-catalyzed reactions extensively used in current organic synthesis for construction of...     

Stereoselective Synthesis of Trisubstituted Vinylboronates from Ketone Enolates Triggered by 1,3‐Metalate Rearrangement of Lithium Enolates

An unprecedented stereoselective synthesis of trisubstituted vinylboronates is reported to proceed by direct borylation of lithium ketone enolates under transition‐metal‐free conditions. The stereospecific C?O borylation of lithium enolates was triggered by a carbonyl‐induced 1,3‐metalate rearrangement via a C‐bound boron enolate. DFT calculations and control experiments revealed that the stereoselectivity is controlled by sterics. A variety of stereospecific trisubstituted vinylboronates, together with several tetrasubstituted vinylboronates, were conveniently synthesized with the newly developed methodology. Based on the transformation of stereospecific vinylboronate, a single isomer of Dienestrol was efficiently obtained.     

New Chiral Calixsalen Chromium Complexes: Recyclable Asymmetric Catalysts

A chiral N,N′‐bis(salicylidene)ethylenediamine (salen) polymer has been prepared by a condensation reaction between a thiophenedisalicyladehyde derivative and (S,S)‐cyclohexane‐1,2‐diamine. This polymeric compound was demonstrated to possess a cyclic structure with two to five repetitive units. The addition of chromium(II) salts led to the generation of a chiral catalyst that could be recovered as an insoluble powder. The performance of this new calixsalen‐type catalyst was examined in various transformations, particularly in its ability to promote nucleophilic epoxide ring opening under heterogeneous conditions. The target products were obtained in high yields and with improved selectivity compared with those obtained by using analogous linear polymers. The arrangement of the catalytic sites in the cyclic structure is probably more suitable for the necessary cooperative bimetallic pathway of this demanding reaction. The catalyst could be successfully recycled. This approach represents the first use of calixsalen complexes under heterogeneous catalytic conditions.     

Stereoselective Aminoxylation of Biradical Titanium Enolates with TEMPO

A highly efficient and straightforward aminoxylation of titanium(IV) enolates from (S)‐N‐acyl‐4‐benzyl‐5,5‐dimethyl‐1,3‐oxazolidin‐2‐ones with TEMPO has been developed. A wide array of functional groups on the acyl moiety, including alkyl and aryl substituents, olefins, esters, or α‐cyclopropyl, as well as α‐trifluoromethyl groups, are well tolerated. This transformation can therefore produce the α‐aminoxylated adducts in excellent yields with high diastereomeric ratios (d.r.). In turn, parallel additions to the α,β‐unsaturated N‐acyl counterparts give the corresponding γ‐adducts with complete regioselectivity in moderate to good yields. Removal of the piperidinyl moiety or the chiral auxiliary converts the resultant adducts into enantiomerically pure α‐hydroxy carboxyl derivatives, alcohols, or esters in high yields under mild conditions. Finally, a new mechanistic model based on the biradical character of the titanium(IV) enolates has been proposed.