Benzyl Bromide → 3-Benzyloxy-4-methoxybenzaldehyde

HRID 1684057Notes

Reaction equation

C[C@H]1[C@@]23C(O[C@H](C2)C[C@@H]1C1C=CC2OCOC=2C=1)=CC(=O)C(OC)=C3.[CH2:26](Br)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.[O:34]=[CH:35][C:36]1[CH:44]=[CH:43][C:40]([O:41][CH3:42])=[C:38]([OH:39])[CH:37]=1>>[CH2:26]([O:39][C:38]1[CH:37]=[C:36]([CH:44]=[CH:43][C:40]=1[O:41][CH3:42])[CH:35]=[O:34])[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

Participants

Reactant 3

HCID 7498Benzyl Bromide

HCID 12127Isovanillin

HCID 9819306(2S,4S,5R,5aS)-4-(1,3-Benzodioxol-5-yl)-2,3,4,5-tetrahydro-7-methoxy-5-methyl-8H-2,5a-methano-1-benzoxepin-8-one2×

Product 1

HCID 806713-Benzyloxy-4-methoxybenzaldehyde

Procedure

FIGS. 17 and 18 disclose a procedure for synthesizing futoenone and futoenone derivative compounds. Benzyl bromide (BnBr) is used to protect isovanillin (201) by reaction using phase transfer conditions to yield 3-benzyloxy-4-methoxybenzaldehyde (202). Oxidation of 3-benzyloxy-4-methoxybenzaldehyde (202) with m-chloroperbenzoic acid followed by hydrolysis in refluxing methanol yields 3-benzyloxy-4-methoxyphenol (203). The phenol is placed in toluene and the suspension is treated with n-butyl-lithium to form a precipitate. 1,4-dibromobutene is then added to the reaction and the contents are heated to reflux overnight to form vinylbenzofuran (206). An ester (207) is formed using a Horner-Emmons modified Wittig reaction and is subsequently reduced to the allylic alcohol (208) using diisobutylaluminum hydride. The allylic alcohol can then be epoxidized in a Sharpless epoxidation to form 2-(2,3'-epoxybutanol)-7-benzyloxy-6-methoxydihydrobenzofuran (209).

Workup

customby reaction

Sources & evidence

ORD record: ord-9bc3ed2cf8614ceb856000040b8cc2c3
Source dataset: uspto-grants-1997_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05639782

Reaction notes

Loading…