Adenine → N6-(N-methyl-2-pyrrolidin-ylidene)-9-[(1RS,4SR)-4-hydroxy-cyclopent-2-en-1-yl]adenine

HRID 1780756ノート

反応式

HRID 1780756 の反応式
P(OC(C)C)(OC(C)C)OC(C)C.C([Li])CCC.CCCCCC.[CH3:25][N:26]1[CH2:30][CH2:29][CH2:28][C:27]1=[N:31][C:32]1[N:40]=[CH:39][N:38]=[C:37]2[C:33]=1[NH:34][CH:35]=[N:36]2.N1C(N)=C2C(N=CN2)=NC=1.[O:51]1[C:53]2[CH2:54][CH2:55][CH2:56][C:52]1=2>O1CCCC1.CC(O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN1CCCC1=O.CS(C)=O>[CH3:25][N:26]1[CH2:30][CH2:29][CH2:28][C:27]1=[N:31][C:32]1[N:40]=[CH:39][N:38]=[C:37]2[C:33]=1[N:34]=[CH:35][N:36]2[CH:55]1[CH2:56][CH:52]([OH:51])[CH:53]=[CH:54]1

参加物

12

反応物 6

HCID 190AdenineHCID 8058HexaneHCID 8304Triisopropyl phosphiteHCID 19047329N6-(N-methyl-pyrrolidin-ylidene)adenineHCID 22121731HCID 22121731、化合物HCID 178418339Butyllithium

生成物 1

HCID 67878693N6-(N-methyl-2-pyrrolidin-ylidene)-9-[(1RS,4SR)-4-hydroxy-cyclopent-2-en-1-yl]adenine収率 27.1%

試薬・触媒・溶媒 5

HCID 167845palladium(II) acetate触媒HCID 679Dimethyl Sulfoxide溶媒HCID 3776Isopropanol溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 13387N-methyl-2-pyrrolidone溶媒

実験手順

224 mg (1 mmol) of palladium(II) acetate, 2.5 ml (10 mmol) of triisopropyl phosphite and 1.5 ml of 1.6 molar n-butyllithium solution in n-hexane (2 mmol) are brought together in 40 ml of dry tetrahydrofuran at 0° C. under inert nitrogen gas and the mixture is stirred. After addition of 30 ml of dry dimethylsulfoxide, 4.32 g (20 mmol) of N6 -(N-methyl-pyrrolidin-ylidene)adenine (prepared by reaction of adenine with the diethyl acetal of N-methyl-pyrrolid-2-one in 2-propanol; beige powder, melting point: 248°-251° C.) are added; a solution of 1.64 g (20 mmol) of epoxycyclopentene in 20 ml of dry tetrahydrofuran is then added dropwise in the course of one hour. The solution is stirred at room temperature for 12 hours and then concentrated and the residue is chromatographed over silica gel (methylene chloride/methanol 9/1). 1.62 g (27% of theory) of N6 -(N-methyl-2-pyrrolidin-ylidene)-9-[(1RS,4SR)-4-hydroxy-cyclopent-2-en-1-yl]adenine of melting point 135°-138° C. are obtained in a regiospecific manner. 1H NMR (270 MHz, d6 -DMSO), δ[ppm]: 8.42 (s, 1H), 8.16 (s, 1H), 6.20 (m, 1H), 6.00 (m, 1H), 5.50 (m, 1H), 5.46 (d, 1H), 4.73 (m, 1H), 3.50 (t, 2H), 3.04 (s, 3H), 2.90 (m, 1H), 2.85 (t, 2H), 1.97 (p, 2H), 1.74 (m, 1H). N6 -(N-Methyl-2-pyrrolidin-ylidene)-9-(cyclopent-1-en-3-on-1-yl)adenine of melting point 200°-205° C. is isolated as a by-product (20 mg, 0.3% of theory). 1H NMR (270 MHz, CDCl3), δ[ppm]: 8.64 (s, 1H), 8.13 (s, 1H), 7.19 (m, 1H), 3.53 (t, 2H), 3.34 (m, 2H), 3.20 (s, 3H), 3.07 (t, 2H), 2.65 (m, 2H), 2.10 (p, 2H).

後処理

  1. additionbeige powder, melting point: 248°-251° C.) are added
  2. stirringThe solution is stirred at room temperature for 12 hours
  3. concentrationconcentrated
  4. customthe residue is chromatographed over silica gel (methylene chloride/methanol 9/1)

出典と根拠

ORDレコード
ord-748dfcba98824a7cb055ff27a78ee47d
出典データセット
uspto-grants-1997_05
特許番号
US05631259

反応ノート

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