Toluene → HCID 70117062, compound

HRID 1016269Notes

Reaction equation

HRID 1016269 reaction equation
[CH2:1]([O:8][C:9]1[CH:26]=[CH:25][C:24]2[C@@H:23]3[C@H:14]([C@H:15]4[C@@:19]([CH2:21][CH2:22]3)([CH3:20])[C@@H:18]([OH:27])[C@@H:17]([CH2:28][CH:29]=O)[CH2:16]4)[CH2:13][CH2:12][C:11]=2[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:31]1(C)C=CC=CC=1>N1C=CC=CC=1.C1COCC1.[CH3-].C[Al+]C.[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Cl-].[Ti+3]>[CH2:28]([C@@H:17]1[CH2:16][C@H:15]2[C@H:14]3[C@H:23]([CH2:22][CH2:21][C@:19]2([CH3:20])[C@H:18]1[OH:27])[C:24]1[CH:25]=[CH:26][C:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[CH:10][C:11]=1[CH2:12][CH2:13]3)[CH:29]=[CH2:31]

Participants

6

Reactant 2

HCID 1140Toluene2×HCID 86585979HCID 86585979, compound

Product 1

HCID 70117062HCID 70117062, compoundYield 25%

Reagents, catalysts & solvents 3

HCID 53384502mu-Chlorobis(eta5-cyclopentadienyl)(dimethylaluminum)-mu-methylenetitaniumCatalystHCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 5.3 mg (0.013 mmol) of 27 in anhydrous toluene (99.7 μL), pyridine (1 μL) and THF (33 μL) was stirred at −78° C. as 0.0156 mmol of Tebbe reagent (31 μL of a 0.5 M solution in toluene) was added by syringe. Reaction was stirred at −78° C. for 2 h, allowed to stir at 40° C. for 2 h then at 0° C. for 1 h. Reaction was quenched with 15% NaOH (25 μL), allowed to stir for ½ h, warmed to rt and passed through a 1″ plug of Celite. The filter was washed with EtOAc and the filtrate was concentrated in vacuo. Purification of the residue on a 1×17 cm column of silica gel using hexanes/EtOAc (2:1) followed by hexanes/EtOAc (4:1) gave 1.3 mg (25%) of 28 as a clear colorless oil and 1.8 mg (34%) of recovered 27. Data for 28: TLC, T-6, Rf0.76. 1H NMR (500 MHz, CDCl3) δ 0.83 (s, 3H, H-18), 2.86 (m, 2H, H-6), 3.33 (d, 1H, J=7.4 Hz, H-17α), 5.03-5.12 (m, 2H,═CH2), 5.04 (s, 2H, benzylic), 5.85-5.93 (m, 1H, —CH═CH2), 6.72 d, 1H, J=2.6 Hz, H-4), 6.79 (dd, 1H, J=8.7, 2.6 Hz, H-2), 7.21 (d, 1H, J=8.7 Hz, H-1), 7.31-7.44 (m, 5H, Ar—H).

Workup

  1. additionwas added by syringe
  2. customReaction
  3. stirringto stir at 40° C. for 2 h
  4. waitat 0° C. for 1 h
  5. customReaction
  6. customwas quenched with 15% NaOH (25 μL)
  7. stirringto stir for ½ h
  8. temperaturewarmed to rt
  9. washThe filter was washed with EtOAc
  10. concentrationthe filtrate was concentrated in vacuo
  11. customPurification of the residue on a 1×17 cm column of silica gel

Sources & evidence

ORD record
ord-561db5e272ab4c7cb4d2625c0de24e20
Source dataset
uspto-grants-2002_11
Patent number
US06476012B2

Reaction notes

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