Styrene oxide lithium aluminum hydride

Alkene oxides may also be cleaved by reduction with lithium aluminum hydride as in the preparation of a-phenylethyl alcohol from styrene oxide (9 4%). ... 

A reinvestigation of the stereoselectivity of the reaction between styrene and 2,3,4,5-tetrahydropyridin-l-oxide in chloroform shows a predominance of isomer 63 over 64 (ratio 98 2). Changing the solvent to toluene made no significant difference to the result. The reductive cleavage of the N—O bond of the derived N-methylated isoxazolidine (65) with W2 Raney nickel in methanol gives allosedamine (67) in 90% yield, whereas lithium aluminum hydride reduction of 65 affords 80% allosedamine and 20% sedamine (68) (87BSB57). 

The perhydro-isoxazolo[2,3-fl]pyridine system offers a route to 2,6-disubstituted piperidines. For example, the reaction between styrene and the substituted 3,4,5,6-tetrahydropyridine-l-oxide (69) gives the isoxa-zolidine (70) which, on benzylation, gives 71. This was subjected to reductive cleavage of the N—O bond with lithium aluminum hydride, followed by mesylation of the aminodiol produced. Treatment of the mesylate with lithium triethylborohydride gave the trans-2,6-disubstituted piperidine... 

Hofmann degradation, styrene 468 was formed. Epoxidation of 468 with m-chloroperbenzoic acid from the less hindered side and lithium aluminum hydride reduction gave ( )-epicorynoline (469). Moreover, slow addition of the a-methoxystyrene 471 to isoquinolinium salt 470 gave cycloadduct 472 in 90% yield. The adduct was hydrolyzed by acid and the resultant aldehyde oxidized to naphthoic acid by Jones oxidation. Modified Curtius rearrangement of 473 with added benzyl alcohol afforded benzyl urethane 474, which was reduced by lithium aluminum hydride and formylated with chloral to give 0-methylarnottiamide (475) (Scheme 60). 

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