69489-15-2

Upstream product

• 115156-59-7 (S)-1-((2S,4aS,7R,8aR)-3-Benzyl-4,4,7-trimethyl-octahydro-benzo[e][1,3]oxazin-2-yl)-1-phenyl-propan-1-ol 
• 89556-33-2 2-<(1'S)-1'-hydroxy-1'-phenylpropyl>hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin 
• 168961-28-2 (1S,2R,4S,6S,7R)-4-((S)-1-Hydroxy-1-phenyl-propyl)-7,10,10-trimethyl-3-oxa-5-aza-tricyclo[5.2.1.0^2,6]decane-5-carboxylic acid tert-butyl ester 
• 636599-74-1 (1S,2R,5R,7S,9R)-5-[(1'S)-1'-hydroxy-1'-phenylpropyl]-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane 
• 682352-20-1 (1S,2R,3S,5R,1'R,2'S)-6,6-dimethyl-3-(1'-ethoxy-2'-phenyl-2'-hydroxy-1'-butylsulfanyl)-2-(O-t-butyl-dimethylsilyl-hydroxymethyl)-bicyclo[3.1.1]heptane 
• 6175-45-7 2,2-diethoxyacetophenone 
• 599192-45-7 (1S,2R,5R,7S,9R)-5-benzoyl-10,10-dimethyl-4-oxa-6-thiatricyclo[7.1.1.0^2,7]undecane 
• 682352-09-6 (1S,2R,3S,5R,2'R)-6,6-dimethyl-3-(2'-ethoxy-1'-phenyl-1'-oxo-2'-ethylsulfanyl)-2-hydroxymethyl-bicyclo[3.1.1]heptane 
• 682352-11-0 (1S,2R,3S,5R,2'R)-6,6-dimethyl-3-(2'-ethoxy-1'-phenyl-1'-oxo-2'-ethylsulfanyl)-2-(O-t-butyl-dimethylsilyl-hydroxymethyl)-bicyclo[3.1.1]heptane 
• 266694-57-9 Phenyl-((2R,4aR,7R,8aR)-4,4,7-trimethyl-hexahydro-1-oxa-3-thia-naphthalen-2-yl)-methanone 
• 1074-12-0 phenylglyoxal hydrate 
• 115156-57-5 (2S,4aS,7R,8aR)-2-benzoyl-N-benzyl-4,4,7-trimethyl-octahydro-1,3-benzoxazine 
• 93-55-0 1-phenyl-propan-1-one 
• 872045-33-5 (1-methoxybut-1-en-2-yl)benzene 

Downstream Products

• 2404-42-4 (S)-(-)-2-phenyl-butane-1,2-diol 
• 3966-31-2 (R)-2-hydroxy-2-phenylbutyric acid 
• 24256-91-5 (S)-2-hydroxy-2-phenylbutanoic acid 
• 76496-47-4 (S)-2-hydroxy-2-phenyl-butyric acid methyl ester 
• 89616-49-9 (R)-2-hydroxy-2-phenyl-butyric acid methyl ester 

Relevant academic research and scientific papers

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.

Lithium binaphtholate-catalyzed asymmetric addition of lithium acetylides to carbonyl compounds

The asymmetric addition of lithium acetylides to carbonyl compounds in the presence of a chiral lithium binaphtholate catalyst was developed. A procedure involving the slow addition of carbonyl compounds to lithium acetylides improved the enantioselectivi

Lithium acetylides as alkynylating reagents for the enantioselective alkynylation of ketones catalyzed by lithium binaphtholate

Chiral lithium binaphtholate effectively catalyzed the enantioselective alkynylation of ketones using lithium acetylide as an alkynylating agent. This is the first example of the catalytic enantioselective addition of lithium acetylide to carbonyl compoun

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 synthesis of either enantiomer of α-alkyl-α- hydroxy-α-phenylacetic acids using chiral auxiliaries

The enantioselective synthesis of either enantiomer of α-alkyl- α-hydroxy-α-phenylacetic acids was achieved by using 2-acyloxathianes 1a-c and the mixed acyl-S,O-acetals 7 and 8 as chiral auxiliaries, which can straightforwardly be prepared from (1R)-(-)-myrtenal. This procedure allowed the preparation of the title compounds in >95% enantiomeric excess (ee).

Camphor-derived 2-stannyl-N-Boc-1,3-oxazolidine: A new chiral formylanion equivalent for the asymmetric synthesis of 1,2-diols

Optically pure 2-tributylstannyl-N-Boc-1,3-oxazolidine 6, prepared from the camphor-derived aminoalcohol 5, was converted to diastereomerically pure 2-acyl derivatives 8 in three steps. Reaction of these ketones with Grignard reaagents at -78°C proceeded with high stereoselectivity affording tertiary carbinols which gave 1,2-diols with >96% ee after hydrolysis and reduction of the intermediate α-hydroxy aldehydes. A new deblocking procedure of the t-Boc group is also described.

HIGHLY ENANTIOSELECTIVE SYNTHESES OF α-HYDROXYACIDS USING N-BENZYL-4,4,7α-TRIMETHYL-TRANS-OCTAHYDRO-1,3-BENZOXAZINE AS A CHIRAL ADJUVANT

Addition of Grignard and organolithium reagents to as well as hydride reduction of 2α-benzoyl-N-benzyl-4,4,7α-trimethyl-trans-octahydro-1,3-benzoxazine (2, Y = C6H5CO) and addition of phenylmagnesium bromide to the corresponding 2-acetyl analog (11) proceed in highly diastereoselective fashion to produce virrtually exclusively the diastereomer predicted on the basis of Cram's chelate rule if chelation involves the ring oxygen atom.Mild acid hydrolysis of the adducts followed by selective oxidation produces highly enantiomerically pure α-hydroxyacids with clean recovery of the chiral adjuvant.

Asymmetric Syntheses Based on 1,3-Oxathianes. 2. Synthesis of Chiral Tertiary α-Hydroxy Aldehydes, α-Hydroxy Acids, Glycols (RR'C(OH)CH2OH), and Carbinols (RR'C(OH)CH3) in High Enantiomeric Purity

A chiral 1,3-oxathiane (5) prepared from (+)-pulegone in three steps is converted to diastereomerically pure equatorial 2-acyl derivatives by lithiation, condensation with aldehydes, and Me2SO oxidation.Reaction of the resulting ketones with Grignard reagents at -78 deg C again proceeds highly stereoselectively (diastereomer excess generally above 90percent) according to Cram's rule (cyclic model).The resulting tertiary carbinols when cleaved with NCS/AgNO3 give chiral tertiary α-hydroxy aldehydes, RR'C(OH)CHO, plus a mixture of epimeric sultines which may be readily reconverted to the starting oxathiane.The hydroxy aldehydes have been oxidized to chiral tertiary α-hydroxy acids, RR'C(OH)CO2H, and reduced to primary-tertiary glycols, RR'C(OH)CH2OH, and further to tertiary carbinols, RR'C(OH)CH3, all with over 90percent ee.The opposite enantiomers of these compounds (again >90percent ee) may be obtained by starting with a diastereomeric 1,3-oxathiane (6), also available from (+)-pulegone.The configurations of the chiral products may be deduced from the manner of preparation and the assumption that Cram's rule is valid and agree with prior assignments in the literature.

α-Hydroxyaldehyde and a process for preparing the same

An optically active or racemic α-hydroxyaldehyde represented by the general formula (2), STR1 wherein R1 represents a C6 -C14 aryl group, C1 -C10 alkyl group, C3 -C10 alkenyl group, C2 -C10 alkynyl group, C7 -C14 aralkyl group, or a group containing a functional group in the organic portion of said groups and R2 represents a C1 -C10 alkyl group, C2 -C10 alkenyl group, C2 -C10 alkynyl group, C7-C14 aralkyl group, C6 -C14 aryl group, or a group containing a functional group in the organic portion of these groups, which is an important intermediate for preparation of pharmaceuticals and agricultural chemicals, and prepared by allowing an optically active or racemic compound represented by the general formula (1), STR2 (wherein A represents a C6 -C14 aryl group or a C1 -C4 alkyl or alkoxy group- or halogen-substituted C6 -C14 aryl group and R1 is as defined above) to react with a Grignard reagent, and thereafter hydrolyzing the reaction product.