Dichloromethane → (3R,5S)-1-t-Butoxycarbonyl-5-carboxy-3-methylpyrrolidine-2-one

HRID 2881

反応式

HRID 2881 の反応式
[C:1]([O:5][C:6]([N:8]1[C@H:12]([CH2:13][OH:14])[CH2:11][C@@H:10]([CH3:15])[C:9]1=[O:16])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(#N)C.C(Cl)(Cl)(Cl)Cl.O.I([O-])(=O)(=O)=[O:27].[Na+].ClCCl>[Cl-].[Na+].O.[Ru](Cl)(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[C@H:12]([C:13]([OH:27])=[O:14])[CH2:11][C@@H:10]([CH3:15])[C:9]1=[O:16])=[O:7])([CH3:4])([CH3:2])[CH3:3]

参加物

7

反応物 4

HCID 6344DichloromethaneHCID 22592919water acetonitrile CCl4HCID 22883709(3R,5S)-1-t-butoxycarbonyl-5-hydroxymethyl-3-methylpyrrolidine-2-oneHCID 23667635Sodium periodate

生成物 1

HCID 57159430(3R,5S)-1-t-Butoxycarbonyl-5-carboxy-3-methylpyrrolidine-2-one収率 54%

試薬・触媒・溶媒 2

HCID 61850Ruthenium trichloride触媒HCID 57417360Sodium chloride; water溶媒

実験手順

To a solution of (3R,5S)-1-t-butoxycarbonyl-5-hydroxymethyl-3-methylpyrrolidine-2-one in a solvent mixture of acetonitrile:carbon tetrachloride:water (2:2:3, 266 mL) was added sodium periodate (3 eq, 24.0 g) and ruthenium trichloride (2.2 mol %, 0.174 g). The solution was stirred 2 hr at room temperature and then diluted by the addition of dichloromethane (500 mL) and brine (200 mL). The organic phase was separated and the aqueous phase was extracted with dichloromethane (3 x 200 mL). The combined organic phases were dried over Na2SO4 then celite added. The solution was filtered under suction through a bed of celite and the filtrate was evaporated to give an oily residue which was crystallized in ethyl acetate and hexane to give 5.03 g product (54%). The mother liquor was purified by flash column chromatography on silica gel, eluting with 70% ethyl acetate in hexane (with 1% of formic acid) to give an additional 1.21 g (13%) of the acid (total 67% yield in two steps). 1H NMR (200 MHz, CDCl3): δ 6.65 (br s, 1H), 4.60 (d, J=8.6, 0.9 Hz, 1H), 2.70 (m, 1H), 2.40 (dd, J=12.5, 8.8 Hz, 1H), 2.0 (m, 1H), 1.55 (s, 9H), 1.25 (d, J=7.0 Hz, 3H).

後処理

  1. customThe organic phase was separated
  2. extractionthe aqueous phase was extracted with dichloromethane (3 x 200 mL)
  3. dry with materialThe combined organic phases were dried over Na2SO4
  4. additionthen celite added
  5. filtrationThe solution was filtered under suction through a bed of celite
  6. customthe filtrate was evaporated
  7. customto give an oily residue which
  8. customwas crystallized in ethyl acetate

出典と根拠

ORDレコード
ord-94c314721a7e472a8dbf1f4c15f24609
出典データセット
uspto-grants-1998_03
特許番号
US05731348

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