HCID 12510600, compound → HCID 131720832, compound

HRID 2393926Notes

Reaction equation

[CH3:1][CH:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][C:5](=[O:10])[CH:4]=[CH:3]1.[C:11]([C:15]1[C:20]([O:21][SiH:22]([CH3:24])[CH3:23])=[C:19]([Br:25])[C:18]([O:26][CH3:27])=[CH:17][C:16]=1[CH2:28]C1C(=O)C=CCC1(C)C)([CH3:14])([CH3:13])[CH3:12]>>[C:11]([C:15]1[C:20]([O:21][SiH:22]([CH3:23])[CH3:24])=[C:19]([Br:25])[C:18]([O:26][CH3:27])=[CH:17][C:16]=1[CH2:28][C@@H:6]1[C:5](=[O:10])[CH:4]=[CH:3][C@@H:2]([CH3:1])[C:7]1([CH3:9])[CH3:8])([CH3:14])([CH3:13])[CH3:12]

Participants

Reactant 2

HCID 12510600HCID 12510600, compound

HCID 178488804HCID 178488804, compound

Product 1

HCID 131720832HCID 131720832, compound

Procedure

This compound was prepared from 4,5,5-trimethylcyclohex-2-en-1-one (10) (169 mg, 1.22 mmol) in the manner previously described for benzylated enone 11, affording 0.337 g (59%) of the less polar trans diastereomer as a colorless, oily solid, along with 22 mg (4%) of the more polar cis diastereomer as a colorless, oily solid, separable by flash column chromatography. The relative stereochemistry of each respective diastereomer was confirmed by nOe NMR experiments. 1H NMR (400 MHz, CDCl3) δ 0.21 and 0.23 [2s, 2×3H, Si(CH3)2 ], 0.98 [s, 9H, SiC(CH3)3 ], 0.90 and 1.10 (2s, 2×3H, geminal-CH3 's), 1.11 (d, 3H, CHCH3), 2.45 (dd, 1H), 2.53 (ddd, 1H), 2.72 and 2.97 (d of ABq, 2H, benzylic-H's), 3.81 (s, 3H, OCH3), 5.87 (dd, 1H, 2-H), 6.55 (dd, 1H, 3-H), 6.64 (s, 1H, Ar--H), 6.93 ppm (s, 1H, Ar--H).

Workup

customaffording 0.337 g (59%) of the less polar trans diastereomer as a colorless, oily solid

Sources & evidence

ORD record: ord-23a8f8c3b3d140a5a471036688195d2d
Source dataset: uspto-grants-1998_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05808139

Reaction notes

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