Allyl?chloride?is?toxic.?Allyl?chloride?(162.8?mL,?2?mol)?was?added?to?a?solution?of?tetrahydroxymethylmethane?(13.6?g,?0.4?mol?OH?groups),?tetrabutylammonium?bromide?(TBAB)?as?phase‐transfer?catalyst,?and?NaOH?(80?g,?2?mol)?in?distilled?water?(80?mL),?and?the?reaction?mixture?was?then?stirred?for?24?h?at?50?°C.?After?the?addition?of?toluene?(400?mL),?the?organic?phase?was?separated,?dried?over?MgSO4,?filtered,and?concentrated?under?vacuum.?The?crude?product?was?further?purified?by?column?chromatography?(silica?gel,?petroleum?ether/ethyl?acetate?10:1?to?1:1)?to?give?a?colorless?oil.?In?some?cases?the?product?had?a?tendency?to?slowly?polymerize?(especially?at?higher?generations).?For?long‐term?storage,?it?was?necessary?to?keep?the?allyl?ether?product?under?an?inert?atmosphere?at??20?°C.
Ozone?was?bubbled?through?a?solution?of?compound?3?(2.82?g,?6.88?mmol)?in?dichloromethane?methanol?(150?mL,?1:1)?at??78?°C?until?the?reaction?mixture?turned?blue,?and?the?complete?consumption?of?the?olefin?was?then?verified?by?TLC.?After?the?removal?of?residual?ozone?by?bubbling?nitrogen?through?the?solution?for?25?min,?excess?dimethyl?sulfide?was?added?at??78?°C?and?the?resulting?solution?was?then?allowed?to?warm?to?room?temperature?and?then?concentrated.?The?oily?residue?was?dissolved?in?ethanol?(100?mL)?and?cooled?to?0?°C?(ice?water?bath).?Sodium?borohydride?(3.90?g,?100?mmol)?was?added?in?portions.?After?the?reaction?mixture?was?allowed?to?reach?room?temperature,?it?was?stirred?for?a?further?24?h.?Water?(50?mL)?was?added?and?the?reaction?mixture?was?acidified?with?20%?HCl?to?pH?6?(pH?paper),?then?filtered.?The?filtrate?was?concentrated?and?the?residue?was?extracted?with?dichloromethane?(3?×?30?mL).?The?combined?extracts?were?dried?(MgSO4)?and?concentrated.?Purification?of?the?residue?by?flash?column?chromatography?(pure?EtOAc,?Rf?0.28)?afforded?the?title?compound?as?a?viscous?colorless?oil?(2.35?g,?81%).
