69489-14-1

Upstream product

• 81968-48-1 1-((7aS)-2-phenyl-(7ar)-hexahydro-pyrrolo[1,2-c]imidazol-3ξ-yl)-ethanone 
• 1074-12-0 phenylglyoxal hydrate 
• 156365-81-0 (2S,4S,5R)-4-methyl-2-(1-oxo-1-phenyl)methyl-5-phenyl-3-tert-butoxycarbonyloxazolidine 
• 135033-57-7 2-(1-Hydroxy-1-phenylethyl)-3-oxa-1-azabicyclo<3.3.0>octane 
• 591-51-5 phenyllithium 
• 108-86-1 bromobenzene 
• 34713-70-7 2-Phenylpropanal 
• 917-64-6 methyl magnesium iodide 
• 78146-52-8 phenylglyoxal monohydrate 
• 64030-44-0 (2S)-2-(anilinomethyl)pyrrolidine 
• 135033-55-5 (2R)-Benzoyl-3-oxa-1-azabicyclo<3.3.0>octane 
• 1075-06-5 2,2-dihydroxy-1-phenyl-ethanone 
• 115156-57-5 (2S,4aS,7R,8aR)-2-benzoyl-N-benzyl-4,4,7-trimethyl-octahydro-1,3-benzoxazine 

Downstream Products

• 2406-22-6 (R)-1-phenyl-1,2-ethanediol 
• 13448-80-1 methyl R-(-)-atrolactate 
• 13448-81-2 (S)-methyl atrolactate 
• 13113-71-8 (S)-Atrolactic acid 
• 3966-30-1 (R)-Atrolactic acid 

Relevant academic research and scientific papers

Nucleophilic additions on acetyldioxanes derived from (?)-(1R)-myrtenal used as chiral auxiliaries: substituent effects on the stereochemical outcome

The synthesis of acetyldioxanes 4 and 9a starting from (?)-(1R)-myrtenal is described. The products were treated with a representative series of nucleophilic reagents (RMgX, RLi, NaBH4 and LiAlH4) to assess the effect of the substituent at C-3 on the stereochemical outcome. It was observed that the nucleophiles preferred the re-face of the C[dbnd]O group when the equatorial substituent at C-3 was a methyl group, whereas a phenyl group at the same position induced the addition through the si-face, thus allowing access to either desired stereochemistry of a final product. This behavior suggests that the formation of the expected Cram-chelated coordination complex takes a coplanar orientation with the C-3 equatorial substituent. Moreover, Grignard reagents were the most stereoselective nucleophiles. The stereochemistry of the addition was established by X-ray diffraction and chemical correlation.

Enantioselective, Lewis Base-Catalyzed Carbosulfenylation of Alkenylboronates by 1,2-Boronate Migration

A catalytic, enantioselective method for the preparation of chiral, non-racemic, alkylboronic esters bearing two vicinal stereogenic centers is described. The reaction proceeds via a 1,2-migration of a zwitterionic thiiranium-boronate complex to give excl

Enantioselective fluorination of α-branched aldehydes and subsequent conversion to α-hydroxyacetals via stereospecific C-F bond cleavage

The highly enantioselective fluorination of α-branched aldehydes was achieved using newly developed chiral primary amine catalyst 1. Furthermore, the C-F bond cleavage of the resulting α-fluoroaldehydes proceeded smoothly under alcoholic alkaline conditio

Me2Zn-Mediated Catalytic Enantio- and Diastereoselective Addition of TosMIC to Ketones

The first catalytic asymmetric addition of TosMIC to unactivated ketones is presented. A combination of Me2Zn and aminoalcohol catalyst promoted the aldol addition/cyclization reaction to render oxazolines possessing a fully substituted stereocenter with excellent yields (up to 92 %), high enantioselectivities (up to 96 %), and complete diastereoselectivity. The chiral oxazolines were then used to give, after a straightforward acid hydrolysis, enantioenriched building blocks bearing tertiary alcohol motifs such as hydroxylaldehydes, hydroxylacids, and hydroxylesters without racemization.

A simple primary amine catalyst for enantioselective α-hydroxylations and α-fluorinations of branched aldehydes

A new primary amine catalyst for the asymmetric α-hydroxylation and α-fluorination of α-branched aldehydes is described. The products of the title transformations are generated in excellent yields with high enantioselectivities. Both processes can be performed within short reaction times and on gram scale. The similarity in results obtained in both reactions, combined with computational evidence, implies a common basis for stereoinduction and the possibility of a general catalytic mechanism for α-functionalizations. Promising initial results in α-amination and α-chlorination reactions support this hypothesis.

Alkyl 2-(2-benzothiazolylsulfinyl)acetates as useful synthetic reagents for alkyl 4-hydroxyalk-2-enoates by sulfinyl-Knoevenagel reaction

Isopropyl, ethyl, and methyl 2-(2-benzothiazolylsulfinyl)acetates have been found to be useful synthetic reagents for sulfinyl-Knoevenagel reaction with various aldehydes to give directly the corresponding 4-hydroxyalk-2-enoates [R′CH(OH)CHCHCO2R], which are ubiquitous structures in biologically active natural products and useful building blocks for organic synthesis of chiral compounds. From the optically pure (R)-2-(2- benzothiazolylsulfinyl)acetates (>99% ee) prepared by the enzymatic kinetic resolution of (±)-2-(2-benzothiazolylsulfinyl)acetates, optically active 4-hydroxyalk-2-enoates (up to 91% ee) have been obtained in good yields.

Catalytic asymmetric dihydroxylation of enamides and application to the total synthesis of (+)-tanikolide

Asymmetric dihydroxylation of β,β- disubstituted enamides afforded chiral tertiary-alcohol-containing α-hydroxyaldehydes and 1,2-diols with high enantioselectivity (see scheme). This method was applied to the total synthesis of the antifungal natural prod

Enantioselective alkynylation of carbonyl compounds with trimethoxysilylalkynes catalyzed by lithium binaphtholate

Enantioselective alkynylation of aldehydes and ketones was accomplished using trimethoxysilylalkynes as alkynylating reagents and lithium 3,3′-diphenylbinaphtholate as a catalyst. Optically active propargylic alcohols were obtained in good to high chemica

Preparation of substituted enol derivatives from terminal alkynes and their synthetic utility

Stereodefined enol derivatives of aldehydes are prepared from terminal alkynes. Specifically, terminal alkynes are known to undergo Cp2ZrCl2-catalyzed methylalumination. Here, we show that the resultant vinylalanes can be oxygenated with peroxyzinc species to generate trisubstituted enolates. Electrophilic trapping with carboxylic anydrides or silyl triflates yields trisubstituted enol esters or silanes, respectively. The tandem carbometalation/oxygenation tolerates free and protected alcohols, heterocycles, olefins, and nitriles. Stereodefined enol esters can undergo asymmetric dihydroxylation to yield optically active α-hydroxy aldehydes. Reduction with NaBH4 provides the diols of 1,1-disubstituted olefins in excellent ee. An application of this methodology to the enantioselective synthesis of the insect pheromone frontalin is presented. Finally, α-hydroxy aldehydes are shown to undergo homologation to a terminal alkyne, reductive amination, oxidation and olefination. Preliminary results indicate that tandem carbometalation/amination can be accomplished with azodicarboxylates. In this way, ene-hydrazines are formed in excellent yield. Copyright

New 2-acyl-1,3-dioxane derivatives from (1R)-(-)-myrtenal: stereochemical effect on their relative ability as chiral auxiliaries

Four 3,10-pinanediol derivatives 1a-d, prepared in 50-72% global yields from (1R)-(-)-myrtenal 2, were treated with (RO)2CHCOR3 (R3 = CH3, Ph) to afford 2-acyl-1,3-dioxanes 3a-f. The latter were submitted to nucleophilic additions using several Grignard reagents to mainly afford carbinols generated by re diastereofacial attack (85-99% yield, ≥88:12 dr). The lowest diastereoselectivity was observed when PhLi or hydrides were used as nucleophiles. Only an equatorial substituent at C-3 modifies the diastereoselectivity of the nucleophilic additions.