all reagents and solvents were obtained from 
 commercial suppliers and were used as received without further purification . 

nmr spectra were recorded on a 400 mhz ( h ) , 100 mhz ( c ) nmr spectrometer at 25 c .
chemical shifts (  ) 
 are reported in parts per million referenced to the nmr solvent residual 
 peak , and coupling constants ( j ) are reported in 
 hertz .
all of the reactions were monitored using tlc and 
 lc  ms ( conducted using an ion - trap mass spectrometer system 
 coupled with an hplc system ) .
melting points were acquired in triplicate using an 
 automatic melting point instrument and are reported as ranges .
ir 
 spectra were recorded on an ft - ir spectrometer as a neat oil or solid . 

a 500 ml three - neck flask 
 with a stir 
 bar was oven - dried and charged with isopropyl methyl ketone ( 80 g , 
 79.8 mmol ) dissolved in meoh ( 150 ml ) .
br2 ( 140 g , 87.8 mmol ) 
 was added dropwise to the reaction mixture over a period of 30 min , 
 after which time the mixture was allowed to stir for 3 h. water ( 200 
 ml ) was added , and the reaction mixture was allowed to stir overnight . 

the contents were transferred into a separatory funnel containing 
 water ( 600 ml ) , and this solution was extracted with ether ( 3  
 250 ml ) .
the collected organic layers were washed with water ( 3  
 250 ml ) , nahco3 ( 1  250 ml ) , and brine ( 1  
 250 ml ) , dried over na2so4 , filtered , and evaporated 
 to give 10 as a pale - yellow oil ( 139 g , 97% ) .
h nmr ( cdcl3 , 400 mhz )  3.86 ( s , 2h ) , 2.51 ( d , j = 7.0 hz , 2h ) , 2.202.11 ( m , 1h ) , 0.92 ( d , j = 6.7 hz , 6h ) .
although there was a small amount ( 5% ) 
 of 2 bromide 11 present , the crude material was 
 used directly in the next step .
a mechanical stirrer was attached 
 to a 1000 ml three - neck round - bottom flask .
the flask was then charged 
 with pph3 ( 250 g , 954 mmol ) , to which was added ethyl acetate 
 ( 300 ml ) .
bromomethyl acetate ( 145 g , 947 mmol ) was dissolved in 200 
 ml of ethyl acetate , and this solution was slowly added to the reaction 
 mixture . after the addition was complete , the reaction mixture was 
 allowed to stir overnight .
the fluffy white solid was collected by 
 filtration , washed with ether , and air - dried overnight to give 380 
 g of compound .
the white solid thus obtained was transferred to a 
 1000 ml beaker , to which were added naoh solution ( 1 n , 300 ml ) and 
 water ( 300 ml ) .
the resulting slurry was stirred for 20 min , and then 
 the contents were transferred to a separatory funnel . after extraction 
 with ch2cl2 , the combined organic layers were 
 washed with water and brine , dried over na2so4 , filtered , and evaporated to give white crystalline solid 13 ( 301 g , 96% yield ) .
h nmr ( cdcl3 , 400 mhz )  7.487.65 ( m , 15h ) , 3.60 ( br s , 3h ) , 2.98 
 ( br s , 1h ) .
to an oven - dried 2 l 
 three - neck flask 
 were added 13 ( 224 g , 670 mmol ) and anhydrous toluene 
 ( 750 ml ) . to the flask
ketone 10 ( 60 g , 335 mmol ) dissolved in anhydrous 
 toluene ( 100 ml ) was charged into the addition funnel and then added 
 to the reaction mixture dropwise .
the reaction mixture was heated 
 at 90 c for 3 h to give a thick yellow suspension , which was 
 then cooled and filtered . to the filtrate
was added methyl bromoacetate 
 ( 51 g , 335 mmol ) , and the mixture was stirred at 90 c for 2 
 h. once again the reaction mixture was cooled to give a precipitate , 
 which was filtered , washed with cold toluene , and then evaporated 
 to give a crude oil that upon purification by flash chromatography 
 using hexane / ethyl acetate ( 2:1 ) as the mobile phase gave olefin 5 ( 25 g , 38% yield ) .
h nmr ( cdcl3 , 
 400 mhz )  7.06 ( d , j = 16.0 hz , 1h ) , 6.66 
 ( d , j = 16.0 hz , 1h ) , 3.81 ( s , 3h ) , 2.50 ( d , j = 7.0 hz , 2h ) , 2.242.14 ( m , 1h ) , 0.94 ( d , j = 7.0 hz , 6h ) ; c nmr ( cdcl3 , 100 
 mhz )  199.5 , 166.1 , 139.8 , 130.2 , 52.3 , 50.5 , 24.7 , 22.5 ; ft - ir 
 ( neat ) 2957.7 , 2873.8 , 1729.5 , 1698.5 , 1466.8 , 1436.7 , 1368.7 , 1298.5 , 
 1272.5 , 1196.6 , 1171.5 , 1113.8 , 1062.7 , 1027.7 , 979.6 , 857.8 , 702.8 
 cm . to 
 an oven - dried 500 ml three - neck flask with a stir bar were attached 
 a reflux condenser and an addition funnel .
the assembly was flushed 
 with argon for 15 min and charged with vinylmagnesium chloride ( 199 
 ml , 1.6 m in thf , 320 mmol ) . to this
was added anhydrous et2o ( 100 ml ) , and the reaction mixture was cooled in an ice bath for 
 30 min .
isovaleraldehyde ( 25 ml , 290 mmol ) dissolved in et2o ( 50 ml ) was added dropwise to the reaction mixture under a positive 
 flow of argon with constant stirring over a period of 40 min .
the 
 reaction mixture was allowed to stir overnight with gradual warming 
 to room temperature .
after confirmation of reaction completion by 
 tlc analysis , the reaction mixture was quenched by adding saturated 
 aqueous nh4cl ( 100 ml ) and then transferred to a separatory 
 funnel .
extraction with et2o , washing of the organic layers 
 with water and brine , drying over na2so4 , filtration , 
 and evaporation of solvents gave alcohol 16 ( 25 g , 76% 
 crude ) as a pale - yellow oil .
h nmr ( cdcl3 , 
 400 mhz )  5.905.81 ( m , 1h ) , 5.22 ( td , j = 17.2 , 1.4 hz , 1h ) , 5.08 ( td , j = 10.4 , 1.3 hz , 
 1h ) , 4.194.14 ( br m , 1h ) , 1.791.69 ( m , 1h ) , 1.64 ( br 
 s , 1h ) , 1.491.43 ( m , 1h ) , 1.351.28 ( m , 1h ) , 0.92 ( dd , j = 6.6 , 2.8 hz , 6h ) ; c nmr ( cdcl3 , 100 mhz )  141.6 , 114.3 , 71.5 , 46.2 , 24.5 , 23.0 , 22.3 ; ft - ir 
 ( neat ) 3338.9 , 2955.7 , 2925.8 , 2870.8 , 1644.9 , 1468.8 , 1423.8 , 1384.8 , 
 1367.8 , 1308.9 , 1152.8 , 1091.8 , 1055.8 , 1016.8 , 988.6 , 918.6 , 841.8 , 
 661.8 cm .
note : alcohol 16 is appreciably 
 volatile , so care must be taken while evaporating the solvents after 
 workup .
a round - bottom 
 flask with a stir bar was oven - dried and then flushed with argon for 
 10 min .
methyl acrylate ( 5 equiv ) , grubbs second - generation 
 catalyst ( 0.005 equiv ) , and cui ( 0.006 equiv ) were charged into the 
 flask under a positive flow of argon , and to this mixture was added 
 anhydrous et2o ( 1 m ) .
argon was bubbled through 
 the reaction mixture for 15 min while the assembly was set up for 
 reflux using an oil bath .
after 10 min , alcohol 16 ( 1 
 equiv ) was added , and the mixture was allowed to reflux for 5 h. the 
 reaction was monitored by tlc ( 2:1 hexanes / etoac ; kmno4 staining ) .
after completion of the reaction , the solvents were evaporated , 
 and the crude mixture was purified by flash chromatography using a 
 hexane / etoac ( 2:1 ) solvent system .
the pure fractions were collected 
 together , evaporated , and dried under vacuum to give alcohol 18 ( 75% yield ) as a dark oil .
h nmr ( cdcl3 , 400 mhz )  6.96 ( dd , j = 15.7 , 5.0 
 hz , 1h ) , 6.04 ( dd , j = 15.6 , 1.6 hz , 1h ) , 4.394.34 
 ( br m , 1h ) , 3.75 ( s , 3h ) , 1.79 ( obscured d , 2h ) , 1.77 ( d , j = 5.2 hz , 1h ) , 1.541.46 ( m , 1h ) , 1.411.34 
 ( m , 1h ) , 0.95 ( d , j = 7.0 hz , 6h ) ; c 
 nmr ( cdcl3 , 100 mhz )  167.0 , 150.9 , 119.4 , 69.4 , 
 51.7 , 45.7 , 24.5 , 23.1 , 22.1 ; ft - ir ( neat ) 3441.9 , 2955.7 , 2870.8 , 
 1724.6 , 1704.5 , 1658.7 , 1467.8 , 1436.7 , 1385.8 , 1367.8 , 1304.6 , 1276.6 , 
 1194.7 , 1168.5 , 1078.7 , 1035.7 , 983.6 , 926.8 , 863.8 , 840.8 , 714.8 
 cm .
mno2 ( 106 g , 1.22 mol ) was 
 heated in an oven at 100 c overnight and then added to a flask 
 containing 11 ( 30 g , 175 mmol ) in ch2cl2 ( 200 ml ) .
the reaction mixture was allowed to stir for 10 
 h , after which conversion was complete by tlc analysis .
the solvents were evaporated to give pure product 5 ( 23 g , 79% yield ) as a pale - yellow oil .
the h nmr , c nmr , and ft - ir data matched those listed above for the 
 material prepared by the previous method .
an oven - dried 100 ml flask with a stir bar was 
 flushed with argon for 15 min and charged with vinylmagnesium chloride 
 ( 18 ml , 1.6 m in thf , 28 mmol ) . to this solution
was added anhydrous 
 et2o ( 30 ml ) , and the reaction mixture was cooled in an 
 ice bath for 30 min .
aldehyde ( 25 mmol ) dissolved in et2o ( 10 ml ) was added dropwise to the reaction mixture under a positive 
 flow of argon with constant stirring over a period of 5 min .
the reaction 
 mixture was allowed to stir overnight with eventual warming to room 
 temperature .
after confirmation of reaction completion by tlc analysis , 
 the reaction mixture was quenched by adding saturated aqueous nh4cl ( 100 ml ) and then transferred to a separatory funnel .
extraction 
 with et2o , washing of the organic layers with water and 
 brine , drying over na2so4 , filtration , and evaporation 
 of solvents gave the desired alcohol , which was purified by flash 
 chromatography using an appropriate hexane / etoac gradient .
colorless oil ( 2.1 
 g , 58% yield ) ; h nmr ( cdcl3 , 400 mhz )  
 7.367.33 ( m , 2h ) , 7.287.25 ( m , 
 3h ) , 6.005.92 ( m , 1h ) , 5.27 ( td , j = 17.2 , 
 1.4 hz , 1h ) , 5.16 ( td , j = 10.5 , 1.3 hz , 1h ) , 4.404.35 
 ( br m , 1h )
, 2.932.88 ( m , 1h ) , 2.842.79 ( m , 1h ) ; c nmr ( cdcl3 , 100 mhz )  140.1 , 137.7 , 129.6 , 
 128.5 , 126.6 , 115.0 , 73.7 , 43.8 ; ft - ir ( neat ) 3376.8 , 3063.9 , 3027.9 , 
 2919.9 , 1644.9 , 1603.9 , 1495.8 , 1454.8 , 1424.8 , 1117.8 , 1076.8 , 1029.6 , 
 990.6 , 921.6 , 854.8 , 744.5 , 697.3 , 668.6 cm .
brown 
 oil ( 1.95 g , 68% yield ) ; h nmr ( cdcl3 , 400 
 mhz )  7.42 ( d , j = 8.4 hz , 2h ) , 7.19 
 ( d , j = 8.2 hz , 2h ) , 5.985.90 ( m , 1h ) , 5.29 
 ( td , j = 17.1 , 1.2 hz , 1h ) , 5.16 ( td , j = 10.3 , 1.2 hz , 1h ) , 5.10 ( br , 1h ) , 2.04 ( br s , 1h ) ; c nmr ( cdcl3 , 100 mhz )  141.5 , 139.8 , 131.6 , 128.0 , 
 1221.6 , 115.7 , 74.7 ; ft - ir ( neat ) 3342.8 , 2981.9 , 2871.9 , 1640.9 , 
 1591.8 , 1485.6 , 1401.7 , 1241.8 , 1191.8 , 1100.8 , 1070.6 , 1033.7 , 1009.4 , 
 986.5 , 924.4 , 815.5 , 794.5 , 719.6 cm . for other metathesis 
 reactions , the same procedure as used for the synthesis of alcohol 18 was followed using the appropriate acrylate and olefin 
 reactants .  
pale - yellow oil ( 0.300 g , 87% yield ) ; h nmr ( cdcl3 , 400 mhz )  7.377.33 ( m , 2h ) , 7.307.23 
 ( m , 3h ) , 7.03 ( dd , j = 15.7 , 4.1 hz , 1h ) , 6.09 ( dd , j = 15.7 , 1.8 hz , 1h ) , 4.574.54 ( br m , 1h ) , 3.76 
 ( s , 1h ) , 2.992.95 ( m , 1h ) , 2.842.78 ( m , 1h ) ; c nmr ( cdcl3 , 100 mhz )  166.9 , 149.1 , 136.7 , 
 129.5 , 128.7 , 127.0 , 120.2 , 71.7 , 51.7 , 43.2 ; ft - ir ( neat ) 3446.9 , 
 3028.9 , 2950.9 , 1704.5 , 1658.7 , 1602.9 , 1495.8 , 1454.8 , 1435.7 , 1309.6 , 
 1273.5 , 1195.6 , 1166.5 , 1100.6 , 1076.7 , 1030.6 , 983.6 , 926.7 , 855.7 , 
 823.8 , 746.6 , 698.3 cm .
data for the e isomer : h nmr 
 ( cdcl3 , 400 mhz )  7.287.21 ( m , 6h ) , 7.187.11 
 ( m , 4h ) , 6.95 ( dd , j = 15.6 , 4.5 hz , 1h ) , 6.02 ( dd , j = 15.6 , 1.7 hz , 1h ) , 5.09 ( s , 2h ) , 4.464.40 ( br 
 m , 1h ) , 2.872.83 ( m , 1h ) , 2.712.65 ( m , 1h ) ; c
nmr ( cdcl3 , 100 mhz )  166.2 , 149.5 , 136.7 , 135.9 , 
 129.5 , 128.7 , 128.5 , 128.2 , 128.1 , 127.0 , 120.3 , 71.8 , 66.3 , 43.2 ; 
 ft - ir ( neat ) 3421.9 , 3030.9 , 2942.9 , 1715.5 , 1655.7 , 1603.9 , 1454.7 , 
 1377.8 , 1302.6 , 1266.5 , 1159.4 , 1100.6 , 1077.7 , 1027.6 , 982.6 , 908.8 , 
 855.8 , 735.5 , 695.2 cm ; hrms ( es - tof ) m / z calcd for c18h18o3na [ m + na ] 305.1154 , found 305.1154 .
off - white solid ( 0.326 g , 78% 
 yield ) ; mp 65.071.9 c ; h nmr ( cdcl3 , 400 mhz ) 
7.377.33 ( m , 2h ) , 7.297.24 ( m , 
 3h ) , 6.92 ( dd , j = 15.6 , 4.7 hz , 1h ) , 6.00 ( dd , j = 15.6 , 1.7 hz , 1h ) , 4.544.49 ( br m , 1h ) , 2.992.94 
 ( m , 1h ) , 2.822.76 ( m , 1h ) , 1.51 ( s , 9h ) ; c nmr 
 ( cdcl3 , 100 mhz )  165.7 , 147.6 , 136.9 , 129.5 , 128.7 , 
 126.9 , 122.5 , 80.5 , 71.8 , 43.3 , 28.1 ; ft - ir ( neat ) 3486.8 , 2977.8 , 
 1693.5 , 1656.6 , 1602.8 , 1493.9 , 1454.8 , 1391.8 , 1367.7 , 1326.7 , 1297.6 , 
 1252.7 , 1213.7 , 1151.6 , 1111.6 , 1071.8 , 1011.7 , 995.7 , 981.7 , 941.7 , 
 863.7 , 848.8 , 746.7 , 710.7 , 698.4 cm ; hrms ( es - tof ) m / z calcd for c15h20o3na [ m + na ] 271.1310 , found 271.1310 .
brown 
 oil ( 0.351 g , 91% yield ) ; h nmr ( cdcl3 , 400 
 mhz )  7.50 ( d , j = 8.5 hz , 2h ) , 7.21 
 ( d , j = 8.4 hz , 2h ) , 7.00 ( dd , j = 15.6 , 4.9 hz , 1h ) , 6.15 ( dd , j = 15.6 , 1.7 hz , 
 1h ) , 5.30 ( br d , j = 4.88 hz , 1h ) , 3.73 ( s , 3h ) ; c nmr ( cdcl3 , 100 mhz )  166.8 , 148.3 , 139.8 , 
 131.9 , 131.9 , 128.2 , 122.3 , 120.1 , 72.8 , 51.8 ; ft - ir ( neat ) 3419.8 , 
 2951.8 , 1703.5 , 1658.6 , 1590.8 , 1486.7 , 1436.6 , 1401.7 , 1274.5 , 1274.5 , 
 1166.5 , 1091.5 , 1070.5 , 1039.6 , 1009.4 , 980.5 , 924.7 , 879.8 , 825.5 , 
 761.7 , 719.7 cm .
pale - yellow solid ( 0.350 g , 
 86% yield ) ; mp 63.565.7 c ; h nmr ( cdcl3 , 400 mhz )  7.50 ( d , j = 8.6 hz , 2h ) , 
 7.387.33 ( m , 5h ) , 7.23 ( d , j = 8.1 hz , 2h ) , 
 7.04 ( dd , j = 15.6 , 5.0 hz , 1h ) , 6.20 ( dd , j = 15.6 , 1.7 hz , 1h ) , 5.35 ( br t , j = 
 3.6 hz , 1h ) , 5.19 ( s , 2h ) , 2.10 ( d , j = 4.0 hz , 1h ) ; c nmr ( cdcl3 , 100 mhz )  166.0 , 148.3 , 139.7 , 
 135.7 , 132.0 , 128.5 , 128.3 , 128.2 , 122.4 , 120.4 , 72.9 , 66.4 ; ft - ir 
 ( neat ) 3461.8 , 2987.8 , 1685.6 , 1646.7 , 1589.8 , 1482.1 , 1454.8 , 1395.7 , 

1382.7 , 1326.7 , 1280.6 , 1218.7 , 1181.6 , 1106.7 , 1088.6 , 1069.6 , 1010.6 , 
 998.6 , 949.7 , 825.7 , 806.7 , 767.7 , 748.5 , 698.5 cm ; hrms ( es - tof ) m / z calcd for c17h15bro3na [ m + na ] 369.0102 , 
 found 369.0102 .
white solid 
 ( 0.315 g , 85% yield ) ; 
 mp 51.053.4 c .
data for the e isomer : h nmr ( cdcl3 , 400 mhz )  7.51 ( d , j = 8.3 hz , 2h ) , 7.24 ( d , j = 8.3 hz , 2h ) , 
 6.89 ( dd , j = 15.6 , 4.8 hz , 1h ) , 6.05 ( dd , j = 15.8 , 2.0 hz , 1h ) , 5.32 ( br t , j = 
 4.6 hz , 1h ) , 2.10 ( d , j = 3.4 hz , 1h ) , 1.48 ( s , 9h ) ; c nmr ( cdcl3 , 100 mhz )  165.5 , 146.5 , 140.0 , 
 131.9 , 128.2 , 122.7 , 122.2 , 80.8 , 72.9 , 28.1 ; ft - ir ( neat ) 3440.8 , 
 2982.8 , 1683.7 , 1652.8 , 1588.9 , 1482.8 , 1454.8 , 1393.8 , 1365.7 , 1340.7 , 
 1315.8 , 1299.8 , 1257.7 , 1234.7 , 1149.5 , 1092.7 , 1066.7 , 1045.7 , 1007.6 , 
 979.6 , 822.5 , 762.7 cm ; hrms ( es - tof ) m / z calcd for c14h17bro3na [ m + na ] 335.0259 , found 335.0259 . to a dry 100 ml flask with a stir bar 
 were added the dess  martin periodinane reagent ( 1.2 equiv ) 
 and dichloromethane ( 1 m ) . to the mixture
was added a solution 
 of the allylic alcohol ( 1.0 equiv ) in minimal dichloromethane .
the 
 reaction mixture was allowed to stir for 30 min and then monitored 
 by tlc to confirm complete transformation of the alcohol to the ketone . 
 following this ,
an equal volume of ether was added , and the mixture 
 was transferred to a separatory funnel containing a saturated nahco3 solution .
the organic layer was washed with na2s2o3 solution , saturated bicarbonate solution , 
 water , and then brine .
evaporation of the solvents gave the desired 
 ketoester in nearly quantitative yield , free of detectable side products .
pale - yellow oil 
 ( 0.111 g , 94% yield ) ; h nmr ( cdcl3 , 400 mhz ) 
  7.377.29 ( m , 2h ) , 7.30 ( obscured 
 d , 1h ) , 7.21 ( obscured d , 2h ) , 7.12 ( d , j = 16.1 
 hz , 1h ) , 6.74 ( d , j = 16.1 hz , 1h ) , 3.92 ( s , 2h ) , 
 3.79 ( s , 3h ) ; c nmr ( cdcl3 , 100 mhz )  
 196.5 , 165.8 , 138.6 , 132.8 , 131.1 , 129.5 , 128.9 , 127.4 , 52.4 , 48.8 ; 
 ft - ir ( neat ) 2952.8 , 1723.5 , 1687.5 , 1603.8 , 1496.7 , 1454.7 , 1438.6 , 
 1414.8 , 1348.7 , 1310.5 , 1256.4 , 1213.6 , 1199.5 , 1170.4 , 1077.6 , 1029.7 , 
 1011.6 , 981.4 , 940.7 , 915.6 , 858.6 , 739.5 , 700.4 cm .
yellow oil ( 0.256 g , 99% 
 yield ) ; h nmr ( cdcl3 , 400 mhz )  7.437.37 
 ( m , 5h ) , 7.357.29 ( m , 3h ) , 7.217.20 ( br , 2h ) , 7.15 
 ( d , j = 15.9 hz , 1h ) , 6.68 ( d , j = 15.9 hz , 1h ) , 5.32 ( s , 2h ) , 3.92 ( s , 2h ) ; c nmr ( cdcl3 , 100 mhz )  196.5 , 165.2 , 138.9 , 135.2 , 132.8 , 131.2 , 
 129.5 , 128.9 , 128.7 , 128.5 , 128.4 , 127.4 , 67.2 , 48.7 ; ft - ir ( neat ) 
 3031.9 , 2961.9 , 1722.5 , 1696.5 , 1636.8 , 1496.8 , 1454.7 , 1376.8 , 1274 , 
 1212.6 , 1165.4 , 1073.7 , 975.5 , 732.5 , 695.2 cm ; hrms ( es - tof ) m / z calcd for c18h16o3na [ m + na ] 303.0997 , 
 found 303.0997 .
yellow 
 oil ( 0.152 g , 86% 
 yield ) ; h nmr ( cdcl3 , 400 mhz )  7.367.33 
 ( m , 2h ) , 7.307.28 ( br d , 1h ) , 7.227.20 ( br d , 2h ) , 
 7.02 ( d , j = 15.7 hz , 1h ) , 6.67 ( d , j = 15.5 hz , 1h ) , 3.91 ( s , 2h ) , 1.50 ( s , 9h ) ; c nmr ( cdcl3 , 100 mhz )  196.9 , 164.6 , 137.7 , 133.6 , 133.0 , 129.5 , 
 128.9 , 127.3 , 82.1 , 48.5 , 27.9 ; ft - ir ( neat ) 2979.8 , 1695.5 , 1636.8 , 
 1496.8 , 1476.8 , 1455.8 , 1393.8 , 1368.6 , 1305.5 , 1257.6 , 1148.2 , 1071.7 , 
 1031.8 , 976.5 , 841.7 , 730.6 , 697.4 cm ; hrms ( es - tof ) m / z calcd for c15h19o3 [ m + h ] 247.1333 , found 247.1334 .
activated 
 mno2 ( 10 equiv , obtained from sigma - aldrich and heated 
 at 100 c overnight before use ) was added to a flask containing 
 the alcohol ( 1 equiv ) in ch2cl2 ( 1 m ) . 

the reaction mixture was allowed to stir for 12 h as the conversion 
 was monitored by tlc analysis .
the solvents were evaporated 
 to give the pure product , typically in high yield and free of detectable 
 side products .
amber solid ( 0.311 g , 83% yield ) ; mp 70.374.6 
 c ; h nmr ( cdcl3 , 400 mhz )  7.62 
 ( d , j = 15.4 hz , 1h ) , 7.28 ( d , j = 8.8 hz , 
 2h ) , 7.08 ( d , j = 8.7 hz , 2h ) , 6.91 ( d , j = 15.4 hz , 1h ) , 3.85 ( s , 3h ) ; c nmr ( cdcl3 , 100 mhz )  188.3 , 165.8 , 135.9 , 135.3 , 132.6 , 132.3 , 130.3 , 
 129.3 , 52.4 ; ft - ir ( neat ) 2952.8 , 1721.6 , 1666.6 , 1626.7 , 1581.6 , 
 1485.8 , 1438.7 , 1396.7 , 1324.7 , 1301.5 , 1220.7 , 1194.7 , 1170.5 , 1067.5 , 
 1007.7 , 993.6 , 943.6 , 833.6 , 821.6 , 755.4 , 661.7 cm .
yellow solid ( 0.250 g , 77% 
 yield ) ; mp 97.2101.3 c ; h nmr ( cdcl3 , 400 mhz )  7.88 ( d , j = 5.8 hz , 1h ) , 7.86 ( d , j = 8.6 hz , 2h ) , 7.66 ( d , j = 8.6 hz , 2h ) , 7.417.40 ( br m , 5h ) , 6.94 ( d , j = 15.5 hz , 1h ) , 5.29 ( s , 2h ) ; c nmr ( cdcl3 , 100 mhz )  188.4 , 165.3 , 136.2 , 135.3 , 135.2 , 132.7 , 
 132.3 , 130.3 , 129.3 , 128.7 , 128.6 , 128.5 , 128.4 , 67.3 ; ft - ir ( neat ) 
 3064.9 , 2956.8,1717.4 , 1667.5 , 1628.7 , 1582.6 , 1499.9 , 1485.8 , 1455.7 , 
 1397.6 , 1371.7 , 1324.7 , 1292.3 , 1217.8 , 1164.3 , 1111.7 , 1071.5 , 1006.6 , 
 978.6 , 969.4 , 949.6 , 912.7 , 862.7 , 838.6 , 811.8 , 753.2 , 731.7 , 700.4 , 
 663.6 cm .
yellow solid ( 0.300 g , 82% 
 yield ) ; mp 86.690.0 c ; h nmr ( cdcl3 , 400 mhz )  7.86 ( d , j = 7.0 hz , 2h ) , 7.74 ( d , j = 15.5 hz , 1h ) , 7.64 ( d , j = 7.0 hz , 2h ) , 6.80 ( d , j = 15.5 hz , 
 1h ) , 1.53 ( s , 9h ) ; c nmr ( cdcl3 , 100 mhz ) 
  188.8 , 164.6 , 135.4 , 135.0 , 134.9 , 132.2 , 130.4 , 129.1 , 82.1 , 
 28.0 ; ft - ir ( neat ) 2971.8 , 2930.8 , 1709.5 , 1663.6 , 1622.7 , 1582.6 , 
 1566.7 , 1480.8 , 1453.8 , 1397.7 , 1369.7 , 1299.5 , 1285.6 , 1251.7 , 1149.4 , 
 1069.6 , 1004.5 , 969.5 , 864.6 , 837.6 , 756.4 , 697.8 , 666.6 cm ; hrms ( es - tof ) m / z calcd for c14h16bro3 [ m + h ] 311.0205 , 
 found 311.0283 .
 a direct and scalable 
 route to -keto-,-unsaturated 
 esters , useful intermediates in medicinal chemistry and natural products 
 synthesis , is reported . 
 the key step involves the use of grubbs 
 second - generation olefin metathesis catalyst for cross - metathesis 
 of alkyl acrylates and 2 allylic alcohols . 
 the metathesis step 
 is followed by oxidation to give the desired products in high yield 
 on scales of up to 25 g. 
Experimental Section