Diastereoselective sulfa-Michael reactions controlled by a biomass-derived chiral auxiliary

A family of chiral auxiliaries derived from the lignocellulosic biomass pyrolysis product levoglucosenone (LGO) has been screened in the sulfa-Michael reaction. When promoted by inorganic bases with potassium counterions, the auxiliary with geminal benzyl substituents showed diastereoselectivity up to 90:10 for a broad range of α,β-unsaturated esters.     

Diastereoselective alkylation reactions employing a camphor-based chiral oxazinone auxiliary

An almost complete π-face selectivity is obtained in asymmetric alkylation reactions of lithium enolates derived from imide 2 which contains a camphor-based chiral oxazinone auxiliary.     

Diastereoselective alkylation reactions employing a new camphor-based 2-phenylimino-2-oxazolidine chiral auxiliary

A new camphor-based 2-phenylimino-2-oxazolidine chiral auxiliary was prepared and it was shown to be a particularly effective chiral auxiliary for asymmetric alkylations affording high yields and diastereoselectivities. The alkylation products were readily cleaved by simple alkaline hydrolysis to give a-alkylated carboxylic acids in good yield and in almost enatiomerically pure form.     

Highly diastereoselective Diels-Alder reaction using a chiral auxiliary derived from levoglucosenone

[reaction: see text] A new chiral auxiliary derived from levoglucosenone is reported. The compound is obtained by a cycloaddition reaction with 9-methoxy methylanthracene followed by a diastereoselective reduction of the C-2 keto function. The auxiliary has been used as a chiral template in an asymmetric Diels-Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene. The results showed excellent diastereomeric excess even at room temperature when the reaction was promoted by Et(2)AlCl as the Lewis acid.     

Diastereoselective intermolecular Pauson-Khand reactions of chiral cyclopropenes

In this Letter, it is demonstrated that the unusual reactivity of cyclopropenes can increase the scope and utility of intermolecular Pauson-Khand reactions. The well-defined chiral environment of cyclopropenes has a powerful influence on the diastereoselectivity of the reactions and leads to the production of a single cyclopentenone in each of the described cases. The cyclopropane ring strongly influences the stereochemistry of reactions at the enone, and the three-membered ring can subsequently be cleaved under mild conditions. [reaction: see text]     

A chiral auxiliary derived from levoglucosenone in asymmetric Diels-Alder transformations

The Diels-Alder reaction of the acrylate derived from levoglucosenone with cyclopentadiene was studied under several conditions, in the presence and absence of a Lewis acid. The results showed satisfactory diastereomeric excess and the ratio of cycloadducts was found to depend on the reaction conditions. A reversal in stereoselectivity was observed when EtAlCl₂ or Et₂AlCl were employed as Lewis acids.     

Enhanced stereocontrol in Diels-Alder reactions of chiral dienols

This combined experimental-computational investigation demonstrates that the presence of a removable bromine substituent on a diene leads to complete pi-diastereofacial and endo/exo stereoselection in both intermolecular and intramolecular Diels-Alder reactions. The influence of the bromine upon stereoselectivity is dramatic: the cycloaddition of nonbrominated precursor 18E, for example, gives four diastereomeric products in a 55:13:16:16 ratio; the bromine-containing analogue gives one stereoisomer within the limits of detection. The examination of B3LYP/6-31+G(d) transition structures allows an interpretation of these experimental findings. A method for the completely stereoselective synthesis of complimentary diastereomeric products (30Z and 31Z) from the same simple starting materials (28 and 2) is reported. Discrepancies between calculation and experiment in an earlier investigation into the Diels-Alder reaction are explained.     

Diastereoselective magnesium halide-catalyzed anti-aldol reactions of chiral N-acyloxazolidinones.

A chiral auxilliary-based direct aldol reaction is reported. The reactions are catalytic in magnesium salts and are facilitated by silylation with chlorotrimethylsilane. The adducts isolated are in high diastereoselectivity (up to 32:1 dr) and favor the anti-aldol diastereomer B. Reactions are operationally simple and can be run under ambient atmosphere without rigorous exclusion of water. Many of the adducts are highly crystalline and a single diastereomer can be isolated without chromatography.     

A novel design of a levoglucosenone derived chiral auxiliary

A two-step general approach to a new chiral auxiliary starting from levoglucosenone is reported. The compound is obtained by a [4+2] cycloaddition reaction with anthracene followed by a diastereoselective reduction of the C-2 keto function in high overall yield. The auxiliary has been used as chiral template in an asymmetric Diels-Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene and shown to be efficient for asymmetric induction.     

Diastereoface-discriminative metal coordination in asymmetric synthesis: D-pantolactone as practical chiral auxiliary for Lewis acid catalyzed Diels-Alder reactions

TiCl₄-catalyzed Diels-Alder additions of the acrylate of commercial D-pantolactone to cyclopentadiene, isoprene and butadiene proceed with very high diastereofacial selectivity. Practical and mechanistic aspects of these reactions are discussed.     

Asymmetric Diels-Alder reactions catalyzed by a triflic acid activated chiral oxazaborolidine

This paper reports a new method for the generation of chiral Lewis superacids by protonation of a non-Lewis acidic oxazaborolidine (1) with triflic acid. The resulting cationic species (3) are powerful and highly enantioselective catalysts for the Diels-Alder reaction of various 1,3-dienes with alpha,beta-enals. An optimization study (see Table 1) led to the selection of reaction conditions and catalysts (6A and 6B) which are very effective. The reactions are simple to conduct, reproducible, and economical, since only ca. 6 mol % of catalyst is required. In addition, the chiral catalyst precursor is readily recovered for reuse (>95% efficiency) and is commercially available. The broad scope of the process is documented by the 14 examples listed in Table 2. The absolute stereochemical course of the Diels-Alder reactions catalyzed by 6A and 6B was successfully predicted on the basis of the mechanistic principles which have recently been formulated for this type of catalytic enantioselective reaction involving re-face attack by the diene on complex 7. The mode of generation of Lewis superacids 6A and 6B allows an approximate comparison (or scale) connecting the catalytic power Lewis and protic acids.     

AlPO-Catalysed asymmetric Diels-Alder reactions of cyclopentadiene with chiral acrylates

Reactions of cyclopentadiene with several chiral acrylates are studied and compared with the same reactions catalysed by Zn(II)-exchanged K10 montmorillonite. In general, amorphous AlPO₄ is a more efficient catalyst than the clay. In particular, the reaction of cyclopentadiene with (−)-8-phenylmenthyl acrylate leads to 74% diastereomeric excess (d.e.) in methylene chloride at low temperatures. This result constitutes the highest asymmetric induction described to date for a solid-catalysed asymmetric Diels-Alder reaction. When the reactions are carried out in the absence of a solvent a noticeable decrease in selectivity is observed, probably due to an extensive competition of the non-catalysed reaction.     

Utility of a chiral 1,3-dioxane template in stereoselective intramolecular Diels-Alder reactions

The ethylidene acetal of d-erythrose was used as a template for stereoselective IMDA reactions: high endo selectivity and yields in favor of the cis product were observed with 1,3,9-trienes, resulting from a boat transition state. For natural product synthesis, the reaction was successfully applied to a diene with terminal Z-olefin.     

Catalytic asymmetric aza Diels-Alder reactions of hydrazones using a chiral zirconium catalyst

Catalytic asymmetric aza Diels-Alder reactions of acylhydrazones with Danishefsky’s dienes have been developed. A chiral zirconium complex derived from zirconium propoxide and 3,3′,6,6′-I₄BINOL was found to be effective in this reaction, and the desired optically active 2,3-dihydro-4-pyridone derivatives were obtained with high enantioselectivities. Asymmetric formal synthesis of a natural product, coniine, was conducted using this catalytic asymmetric reaction as a key step.     

γ-手性顺式的共轭烯醛与有机锂化合物的立体选择性反应

本文研究了在手性的顺式-γ-氨基-α,β-不饱和醛(7)与有机锂化合物的亲核加成反应中的1,4-不对称诱导效应.结果表明: 7与α-烷氧基乙烯醇锂类化合物的反应导致了优良的非对映立体选择性(d.e. : 60～90%), 而与烷基锂试剂的反应也给出了高度的立体选择性(d.e.: 74～86%). 这说明在这些反应中 , 存在着一种1,4-不对称诱导反应 .     

Design of a new and highly effective chiral auxiliary for Diels-Alder reaction of 1-aminodiene

A theoretical investigation of the facial selectivity of optically active oxazolidin-2-one-substituted dienes has been realized. This analysis enabled the development of (R)-4-phenyloxazolidin-2-thione as a very effective chiral auxiliary for cycloaddition of 1-aminodiene.     

Conformational model for asymmetric Diels-Alder reactions with chiral dienes

1-(O-methylmandeloxy)dienes have significant advantages for asymmetric Diels-Alder reactions, and we now show that high (90%) diastereofacial selectivities can be obtained with these dienes, permitting considerable choice as to dienophile and the presence of additional functionality. We present experimental support, including X-ray structures showing the conformations of three Diels-Alder adducts, for a transition state model which explains the origin of these selectivities. The distinctive characteristics of this model are that the phenyl group is nearly perpendicular to the ester CO, i.e., the PhCCO dihedral angle is near 90°, and that the methoxy group is close to the carbonyl oxygen. These features may have wider applications for chiral control by α-chiral ester groups in other types of reactions. Our results should renew interest in the use of chiral 1-acyloxydienes.     

Synthesis of a simple chiral auxiliary derived from levoglucosenone and its application in a Diels-Alder reaction

The synthesis of a chiral alcohol derived from levoglucosenone has been studied. The alcohol was employed as chiral template in an asymmetric Diels-Alder reaction of the corresponding acrylic ester derivative with cyclopentadiene, and was shown to be an efficient asymmetric inductor. The oxidation reaction detected during the hydrogenation of a secondary allylic alcohol intermediate with Pd/C was also investigated.     

Diastereoselective heterogeneous catalytic hydrogenation of 2-methyl nicotinic acid using pyroglutamate chiral auxiliary

The diastereoselective hydrogenation of 2-methyl nicotinic acid covalently bound to proline ester or pyroglutamic ester over supported metallic catalyst yielded moderate diastereoselectivity (26%). The hydrogenation of the corresponding pyridinium salt was studied and similar de's were achieved.