Cascade radical carbonylations leading to 3-substituted cyclohexanones

Synlett

Volumn , Issue 14, 2006, Pages 2342-2344

  Uenoyama, Yoshitaka ^a   Fukuyama, Takahide ^a   Ryu, Ilhyong ^a  

^a Osaka City University   (Japan)

Author keywords

Allyltributyltin; Carbon monoxide; Casacde reaction; Radical cyclization; Tributyltin radical

Indexed keywords

CYCLOHEXANONE DERIVATIVE; TIN;

ANNULATION REACTION; ARTICLE; CARBONYLATION; CYCLIZATION; RADICAL REACTION; SYNTHESIS;

EID: 33748680088     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2006-949643     Document Type: Article

References (23)

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22. The reaction also gave the product via a 5-exo/allylation sequence in 5% yield. At higher CO pressures, the second carbonylation of the 5-exoradical also took place. Details will be discussed in a full paper.
23. 3-Allyl-3-methylcyclohexanone (2d) A magnetic stirring bar, AIBN (26.2 mg, 0.16 mmol), benzene (3.4 mL), 4-methyl-4-pentenyl bromide (1d; 92.3 mg, 0.56 mmol), and allyltributyltin (400.0 mg, 1.2 mmol) were placed in a 50-mL stainless-steel autoclave. The autoclave was closed, purged three times with CO, pressurized with 50 atm of CO, and then heated at 80 °C for 12 h. Excess CO was discharged at r.t. The solvent was removed under reduced pressure. The residue was purified by flash chromatography on silica gel (hexane→hexane- EtOAc, 10:1) to give 3-allyl-3-methylcyclohexanone (2d; 73.3 mg, 85%).