tert-Butyl hydroperoxide → 1H-Indene-2-carboxylic acid, 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-, methyl ester

HRID 547988

반응식

HRID 547988 반응식
[C@H]1(NCC2C=C(C(C)(C)C)C=C(C(C)(C)C)C=2O)CCCC[C@@H]1NCC1C=C(C(C)(C)C)C=C(C(C)(C)C)C=1[OH:23].[Cl:41][C:42]1[CH:43]=[C:44]2[C:48](=[CH:49][CH:50]=1)[C:47](=[O:51])[CH:46]([C:52]([O:54][CH3:55])=[O:53])[CH2:45]2.C(OO)(C)(C)C>C1(C)C=CC=CC=1.C(#N)C.CC(C)[O-].[Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[Cl:41][C:42]1[CH:43]=[C:44]2[C:48](=[CH:49][CH:50]=1)[C:47](=[O:51])[C:46]([OH:23])([C:52]([O:54][CH3:55])=[O:53])[CH2:45]2

참가 물질

7

반응물 3

HCID 6410tert-Butyl hydroperoxideHCID 110423911H-Indene-2-carboxylic acid, 5-chloro-2,3-dihydro-1-oxo-, methyl ester2회HCID 54475193[(1S,2S)-1,2-cyclohexanediylbis(iminomethylene)]bis[4,6-bis(1,1-dimethylethyl)phenol]

생성물 1

HCID 109775851H-Indene-2-carboxylic acid, 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-, methyl ester수율 84%

시약·촉매·용매 3

HCID 3083750Zirconium(4+) propan-2-olate촉매HCID 1140Toluene용매2회HCID 6342Acetonitrile용매

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온도
55 °C

실험 절차

A chiral zirconium complex was prepared by stirring zirconium(IV) isopropoxide (0.0345 g, 0.089 mmol) with 2,2′-[(1S,2S)-1,2-cyclohexanediylbis(iminomethylene)]bis[4,6-bis(1,1-dimethylethyl)phenol] (Formula IIIc wherein R6 is C(CH3)3, 0.0613 g, 0.11 mmol) in toluene (2 mL) at ambient temperature. After stirring overnight, the homogeneous solution was evaporated to dryness in vacuo, and the residue redissolved in toluene (1.34 g). Methyl 5-chloro-2,3-dihydro-1-oxo-1H-indene-2-carboxylate (0.250 g, 1.11 mmol) (Formula IIa wherein R1 is OCH3 and R4 is Cl) was added to the toluene solution, the solution was heated to 55° C., and then an aqueous solution of tert-butyl hydroperoxide (70%, 0.316 g, 2.46 mmol) was added. After 2 hours at 55° C., the solution was diluted with acetonitrile (11.5 mL) Analysis by quantitative and chiral HPLC showed 100% conversion of methyl 5-chloro-2,3-dihydro-1-oxo-1H-indene-2-carboxylate, forming methyl 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate in 84% yield (84% chemoselectivity) and 84% enantiomeric excess of the 5-enantiomer.

후처리

  1. customA chiral zirconium complex was prepared
  2. customthe homogeneous solution was evaporated to dryness in vacuo
  3. dissolutionthe residue redissolved in toluene (1.34 g)
  4. waitAfter 2 hours at 55° C.

출처 및 근거

ORD 기록
ord-ba27f4b2a4a44d42be309c5ae2a02ef3
출처 데이터셋
uspto-grants-2011_05
특허 번호
US07939685B2

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