Chloroform → HCID 86758620, compound

HRID 1019237Notes

Reaction equation

HRID 1019237 reaction equation
C(Cl)Cl.C(Cl)(Cl)Cl.[CH3:8][C@:9]12[CH2:19][CH2:18][C@@H:17]3[CH2:20][C@:14]1([O:15][C:16]3([CH3:22])[CH3:21])[CH:13]=[CH:12][CH2:11][CH2:10]2.ClC1C=CC=C(C(OO)=[O:31])C=1>C1C=CC=CC=1>[CH3:8][C@:9]12[CH2:19][CH2:18][C@@H:17]3[CH2:20][C@@:14]1([O:15][C:16]3([CH3:22])[CH3:21])[C@H:13]1[O:31][CH:12]1[CH2:11][CH2:10]2

Participants

6

Reactant 4

HCID 6212ChloroformHCID 6344DichloromethaneHCID 70297m-Chloroperbenzoic acidHCID 12073826HCID 12073826, compound2×

Product 1

HCID 86758620HCID 86758620, compound

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

In Scheme III, compound of formula (5) is reduced by metallic hydride complex, preferably LiAlH4, to form compound of formula (Ic-1) in organic solvent such as diethylether, tetrahydrofuran, 1,2-dimethoxyethane, or any other solvent that does not interfere with the reaction at room temperature. Oxidation of compound of formula (Ic-1) by CrO3/pyridine, pyridinum chlorochromate (PCC) or Jones reagent, preferably PCC, produces compound of formula (Ic-2) and the reaction is generally conducted in organic solvent such as methylene chloride, chloroform, benzene or any other solvent that does not interfere with the reaction at room temperature or heated. (1S,6S,9R)6,10,10-trimethyl-11-oxatricyclo[7.2.1.01,6]dodec-2-ene (formula 8) is oxidized by organic peracid, preferably meta-chloroperbenzoic acid, to form (1S,2S,6R,9R)6,10,10-trimethyl-2,3-epoxy-11-oxatricyclo[7.2.1.01,6]dodecane (formula 9) and the reaction is conducted in organic solvent such as diethylether, methylene chloride, chloroform, benzene or any other solvent that does not interfere with the reaction at room temperature or cooled. The thus produced compound (9) is reduced by metallic hydride complex, preferably LiAlH4 to form (1S,3S,6R,9R)6,10,10-trimethyl-11-oxatricyclo[7.2.1.01,6]dodecan-3-one (formula 10) and the reaction is conducted in organic solvent such as diethylether, tetrahydrofuran, 1,2-dimethoxyethane or any other solvent that does not interfere with the reaction at room temperature or cooled with ice bath. Compound of formula (10) is oxidized by CrO3/pyridine, PCC, or Jones reagent, preferably PCC to form (1S,6R,9R)6,10,10-trimethyl-11-oxatricyclo[7.2.1.01,6]dodecan-3-one (formula 11 ) and the reaction is conducted in organic solvent such as methylene chloride, chloroform, benzene or any other solvent that does not interfere with the reaction at room temperature or heated. Compound (11) is reacted with organometallic reagent such as Grignard reagent or organolithium reagent to form compound of formula (Ic-3) and the reaction is conducted in organic solvent such as diethylether, tetrahydrofuran or any other solvent that does not interfere with the reaction at room temperature or cooled with ice bath. Compound of formula (10) react with phosphorous trihalide in the presence of triphenylphosphine to form (1S,3R,6R,9R)6,10,10-trimethyl-3-halo-11-oxatricyclo[7.2.1.01,6]dodecane and the reaction is conducted in anhydrous diethylether and cooled with ice bath or ice-salt mixture.

Workup

  1. customany other solvent that does not interfere with the reaction at room temperature
  2. temperatureheated

Sources & evidence

ORD record
ord-adec355f602342eb95c618cc124ca907
Source dataset
uspto-grants-2002_11
Patent number
US06486201B1

Reaction notes

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