89556-33-2

Upstream product

• 925-90-6 ethylmagnesium bromide 
• 266694-57-9 Phenyl-((2R,4aR,7R,8aR)-4,4,7-trimethyl-hexahydro-1-oxa-3-thia-naphthalen-2-yl)-methanone 
• 79563-59-0 (-)-(1R,2R,5R)-5-methyl-2-(1-mercapto-1-methylethyl)-cyclohexan-1-ol 
• 79618-03-4 (4aR,7R,8aR)-4,4,7-Trimethyl-hexahydro-1-oxa-3-thia-naphthalene 
• 79563-61-4 1-((2R,4aR,7R,8aR)-4,4,7-Trimethyl-hexahydro-1-oxa-3-thia-naphthalen-2-yl)-propan-1-one 

Downstream Products

• 2455-52-9 Toluene-4-sulfonic acid (S)-2-hydroxy-2-phenyl-butyl ester 
• 79563-59-0 (-)-(1R,2R,5R)-5-methyl-2-(1-mercapto-1-methylethyl)-cyclohexan-1-ol 
• 76496-47-4 (S)-2-hydroxy-2-phenyl-butyric acid methyl ester 
• 89616-49-9 (R)-2-hydroxy-2-phenyl-butyric acid methyl ester 
• 24256-91-5 (S)-2-hydroxy-2-phenylbutanoic acid 
• 3966-31-2 (R)-2-hydroxy-2-phenylbutyric acid 
• 53777-08-5 (S)-2-phenyl-butan-2-ol 
• 69489-15-2 (S)-(-)-hydroxy-2-phenylbutanal 
• 2404-42-4 (S)-(-)-2-phenyl-butane-1,2-diol 
• 79563-63-6 (3aR,6R,7aR)-3,3,6-Trimethyl-hexahydro-benzo[d][1,2]oxathiole 2-oxide 

Relevant academic research and scientific papers

Addition of Organometallic Reagents to Acyloxathianes. Diastereoselectivity and Mechanistic Consideration

The addition of methyl- and phenylmagnesium bromide and phenyllithium to 2-(methoxyacetyl)-, 2--, and 2-hexahydro-4,4,7-trimethyl-4H-1,3-benzoxathiin and the corresponding 2'-methyl, 2'-(triisopropylsiloxy)p

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.