169555-83-3

Upstream product

• 105873-74-3 2-oxo-cyclohexanone cyclic (1S,2S)-1,2-bis(methoxymethyl) ethylene acetal 
• 210101-06-7 (1R,2R)-(1,2-dihydroxycyclohexyl)acetonitrile 
• 210101-07-8 ((3aR,7aR)-2,2-Dimethyl-tetrahydro-benzo[1,3]dioxol-3a-yl)-acetonitrile 
• 210101-08-9 ((3aR,7aR)-2,2-Dimethyl-tetrahydro-benzo[1,3]dioxol-3a-yl)-acetaldehyde 
• 210101-09-0 (1R,5R)-1-allyl-3,3-dimethyl-2,4-dioxabicyclo[4.3.0]nonane 
• 6975-71-9 1-cyclohexenylacetonitrile 
• 60308-50-1 2-hydroxycyclohexanone dimer 
• 925462-45-9 carbonic acid allyl ester 2-oxo-cyclohexyl ester 
• 925462-17-5 (R)-2-allyl-2-(tert-butyl-dimethyl-silanyloxy)-cyclohexanone 
• 210101-10-3 (1R,2R)-1-allyl-1,2-cyclohexanediol 
• 169555-82-2 (2S,3S,6S)-6-Allyl-2,3-bis-methoxymethyl-1,4-dioxa-spiro[4.5]decan-6-ol 
• 169737-44-4 (2S,3S,6R)-6-Allyl-2,3-bis-methoxymethyl-1,4-dioxa-spiro[4.5]decan-6-ol 

Relevant academic research and scientific papers

Enantioselective synthesis of α-tertiary hydroxyaldehydes by palladium-catalyzed asymmetric allylic alkylation of enolates

Chiral α-tertiary hydroxyaldehydes are very versatile building blocks in synthetic chemistry. Herein, we report the first examples of a catalytic asymmetric protocol for the synthesis of such compounds from readily available α-halo or α-hydroxy ketones or enol silyl ethers with excellent yields and enantioselectivity. Its synthetic utility is demonstrated in the short, efficient formal synthesis of (S)-oxybutynin. In this process, the chiral ligand controls the regioselectivity as well as the enantioselectivity. Copyright

Enantioselective synthesis of 2-allyl and 2-(3- trimethylsilylpropargyl)-2-hydroxycyclohexanone using osmium-catalyzed asymmetric dihydroxylation

The catalytic asymmetric dihydroxylation of (1-cyclohexenyl) or (1- cyclopentenyl) acetonitrile 5 and 15 with AD-mix-β occurred with good enantiofacial selectivity (87 to 94.7% ee after recrystallization) giving (R,R)-diols in agreement with the mnemonic

Rearrangement of α-hydroxy imines to α-amino ketones: Mechanistic aspects and synthetic applications

In refluxing diglyme, rearrangement of α-hydroxy imines bearing diversely substituted allyl groups or a 3-trimethylsilylpropargyl group on the α-carbon to the nitrogen afforded in good yields α-amino ketones. Migration of allyl or 3-trimethylsilylallyl groups occurred without allylic transposition in contrast to be 1-methylallyl group. In the 3 cases studied, the rearrangement of enantioenriched α-hydroxy imines took place with complete 1,2-chirality transfer. The rearrangement was applied to the preparation of (+)-1-benzyl-1-azaspiro[5.5]undecan-7-one, a precursor in the synthesis of (-)-perhydrohistrionicotoxin.

Thermal rearrangement of enantioenriched α-hydroxy imines -I. Enantiocontrolled synthesis of α-substituted α-amino ketones

Enantioenriched 2-allyl- and 2-(3-trimethylsilylpropargyl)-2-hydroxycyclohexanone were respectively obtained by resolution from the corresponding diastereomeric acetal derived from C2-symmetrical diol or from the camphanate ester. Study of the rearrangement of their corresponding imine derivatives has shown that it occurred with complete retention of the stereogenicity.