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A racemic pentenylation of aldehydes was developed by Fujita and Schlosser. See
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23
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62349131044
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It is noteworthy that optically active ethyl-substituted homoallylic alcohols are exclusively accessed through aldol chemistry
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It is noteworthy that optically active ethyl-substituted homoallylic alcohols are exclusively accessed through aldol chemistry.
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24
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62349135118
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General Procedure for the syn-Selective Boron-Mediated Pentenylation Reaction: To a stirred suspension of t-BuOK (1.1 equiv) and (Z)-2-pentene (2.2 equiv) in THF at -78°C was added n-BuLi (1.1 equiv) dropwise. After complete addition, the reaction mixture was stirred for 5 min at -50°C. The resulting orange solution was then cooled to -78°C and to it, was added dropwise a solution of, )-methoxydiisopinocampheylborane in Et2O (1.35 equiv, 0.5 M in Et2O, After stirring for 30 min at -78°C, boron trifluoride diethyl etherate (1.5 equiv) was added followed by the aldehyde 1 equiv, The reaction mixture was then stirred for an extra 5 h at the same temperature before it was treated with a 3 M solution of NaOH and H2O2 and refluxed for 1 h. The reaction mixture was then extracted with EtOAc, washed with brine, dried over MgSO4 and concentrated under reduced pressure. The crud
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4 and concentrated under reduced pressure. The crude residue was purified by flash column chromatography on silica gel using a gradient of eluents to afford the corresponding homoallylic alcohol.
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25
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62349099596
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Since the (Z)-crotyl potassium species are thermodynamically more stable than the corresponding E-isomer, preferential access to syn-substituted homoallylic alcohols is observed with them. See: (a) Schlosser, A.; Despond, O.; Lehmann, R.; Moret, E.; Rauchschwalbe, G. Tetrahedron 1993, 49, 10175.
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Since the (Z)-crotyl potassium species are thermodynamically more stable than the corresponding E-isomer, preferential access to syn-substituted homoallylic alcohols is observed with them. See: (a) Schlosser, A.; Despond, O.; Lehmann, R.; Moret, E.; Rauchschwalbe, G. Tetrahedron 1993, 49, 10175.
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0001584981
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Riguera, R.3
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29
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62349134819
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Same procedure as previously employed except that the temperature was not raised to -50°C after the addition of n-BuLi.
-
Same procedure as previously employed except that the temperature was not raised to -50°C after the addition of n-BuLi.
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30
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0033612270
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(a) Cossy, J.; Bauer, D.; Bellosta, V. Tetrahedron Lett. 1999, 40, 4187.
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(a) Heathcock, C. H. In Comprehensive Organic Synthesis, Vol. 2; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford, 1991, 181.
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