Npc54264 → [(3-tert-Butyldimethylsilyloxy-4-methoxyphenyl) methoxymethylene](1',7',7'-trimethyl bicyclo[2.2.1]heptane)

HRID 1956124Notes

Reaction equation

HRID 1956124 reaction equation
[Si:1]([O:8][C:9]1[CH:10]=[C:11]([CH:16]=[CH:17][C:18]=1[O:19][CH3:20])[C:12]([O:14][CH3:15])=O)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[C@:21]12([CH3:31])[C:28]([CH3:30])([CH3:29])[CH:25]([CH2:26][CH2:27]1)[CH2:24][C:22]2=O.[H-].[H-].[H-].[H-].[Li+].[Al+3]>O1CCCC1.[Cl-].[Cl-].[Cl-].[Ti+3]>[Si:1]([O:8][C:9]1[CH:10]=[C:11]([CH2:12][O:14][CH:15]=[C:22]2[CH2:24][CH:25]3[C:28]([CH3:30])([CH3:29])[C:21]2([CH3:31])[CH2:27][CH2:26]3)[CH:16]=[CH:17][C:18]=1[O:19][CH3:20])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 9543187Npc54264HCID 11335452Methyl 3-tert-butyldimethylsilyloxy-4-methoxybenzoateHCID 21226445Aluminium lithium hydride

Product 1

HCID 131719861[(3-tert-Butyldimethylsilyloxy-4-methoxyphenyl) methoxymethylene](1',7',7'-trimethyl bicyclo[2.2.1]heptane)

Reagents, catalysts & solvents 2

HCID 10313229titanium(III) trichlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

Methyl 3-tert-butyldimethylsilyloxy-4-methoxybenzoate (170 mg, 0.57 mmol, prepared in Example 1, Step 2 above) and (1R)-(+)-camphor (Aldrich, 120 mg, 0.79 mmol) were mixed and dissolved in anhydrous tetrahydrofuran (THF, 1.98 ml) and 15 coupled as described in the procedure of Example 1, Step 3, above, by using titanium trichloride (1.9 g, 12.32 mmol), LAH (0.22 g, 5.80 mmol) and THF (13.8 ml). The product was purified on a preparative TLC plate (silica gel). Development with hexane/ethyl acetate (10:1) gave the title compound as a mixture of two isomers (58 mg). NMR(δ): 0.18 (s, 6H), 1.00 (s, 15H), 1.29 (s, 3H), 3.23 (s, 1H, minor isomer), 3.30 (s, 2H, major isomer), 3.85 (s, 3H).

Workup

  1. customThe product was purified on a preparative TLC plate (silica gel)

Sources & evidence

ORD record
ord-21c20a77f5dd4a719191cd5a0678ccea
Source dataset
uspto-grants-1998_07
Patent number
US05780249

Reaction notes

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