The lipase-catalyzed enantioselective acetylation of racemic methyl (4S∗,5S∗)-4-aryl-5-hydroxyhex-2(E)-enoates 1a–h was performed and efficient resolutions were achieved (E >400) by using CAL-B. After brosylation of the obtained optically active 1a–h, solvolysis of brosylates 13a–h afforded the corresponding methyl (4S∗,5S∗)-5-aryl-4-hydroxyhex-2(E)-enoates 3a–h (26–94% yield). The yields of 3a and 3c on the solvolysis of the corresponding 13 were 92% and 40%, respectively, while solvolysis of the corresponding tosylate was reported at 70% and 17%, respectively. This procedure is a facile and practical route to the synthesis of bioactive and optically active bisabolane-type sesquiterpenes.(4S,5S)-Methyl 5-hydroxy-4-(2,5-dimethoxyphenyl)hex-2(E)-enoateC15H20O5Ee = 95.2%ee[α]D29=+4.1 (c 1.10, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4S,5S)(4S,5S)-Methyl 5-hydroxy-4-(3,4-dimethoxyphenyl)hex-2(E)-enoateC15H20O5Ee = 98.6%ee[α]D27=+15.1 (c 1.26, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4S,5S)(4S,5S)-Methyl 5-hydroxy-4-(2,5-dimethoxy-4-methylphenyl)hex-2(E)-enoateC16H22O5Ee = 99.8%ee[α]D29=+10.5 (c 1.36, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4S,5S)(4S,5S)-Methyl 5-acetoxy-4-(4-methoxyphenyl)hex-2(E)-enoateC16H20O5Ee = 99.8%ee[α]D21=-5.5 (c 2.44, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4R,5R)(4S,5S)-Methyl 5-acetoxy-4-(2-methoxy-4-methylphenyl)hex-2(E)-enoateC17H22O5Ee = 98.5%ee[α]D23=+1.8 (c 1.12, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4R,5R)(4S,5S)-Methyl 5-hydroxy-4-(4-methoxyphenyl)hex-2(E)-enoateC14H18O4Ee = >99.9%ee[α]D23=+21.2 (c 2.07, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4S,5S)(4S,5S)-Methyl 5-hydroxy-4-(2-methoxy-4-methylphenyl)hex-2(E)-enoateC15H20O4Ee = >99%ee[α]D23=+2.0 (c 1.10, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4S,5S)(4S,5S)-Methyl 5-hydroxy-4-(4-methoxy-2-methylphenyl)hex-2(E)-enoateC15H20O4Ee = >99%ee[α]D29=-14.2 (c 1.00, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4S,5S)(4S,5S)-Methyl 5-hydroxy-4-(2-methoxy-5-methylphenyl)hex-2(E)-enoateC15H20O4Ee = 99.3%ee[α]D27=+17.6 (c 1.01, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4S,5S)(4S,5S)-Methyl 5-hydroxy-4-(3-methoxy-4-methylphenyl)hex-2(E)-enoateC15H20O4Ee = 98.2%ee[α]D27=-1.7 (c 1.01, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4S,5S)(4S,5S)-Methyl 5-acetoxy-4-(4-methoxy-2-methylphenyl)hex-2(E)-enoateC17H22O3Ee = 99.8%ee[α]D29=+18.6 (c 1.11, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4R,5R)(4S,5S)-Methyl 5-acetoxy-4-(2-methoxy-5-methylphenyl)hex-2(E)-enoateC17H22O5Ee = 98.2%ee[α]D27=-10.0 (c 1.01, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4R,5R)(4S,5S)-Methyl 5-acetoxy-4-(3-methoxy-4-methylphenyl)hex-2(E)-enoateC17H22O5Ee = 99.8%ee[α]D23=+12.5 (c 1.07, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4R,5R)(4S,5S)-Methyl 5-acetoxy-4-(2,5-dimethoxyphenyl)hex-2(E)-enoateC17H22O6Ee = 98.2%ee[α]D25=+6.5 (c 1.03, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4R,5R)(4S,5S)-Methyl 5-acetoxy-4-(3,4-dimethoxyphenyl)hex-2(E)-enoateC17H22O6Ee = 98.0%ee[α]D27=+11.2 (c 1.07, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4R,5R)(4S,5S)-Methyl 5-acetoxy-4-(2,5-dimethoxy-4-methylphenyl)hex-2(E)-enoateC18H24O6Ee = 99.8%ee[α]D14=+5.6 (c 0.36, CHCl3)Source of chirality: enzymatic resolutionAbsolute configuration: (4R,5R)(4S,5S)-Methyl 4-hydroxy-5-(4-methoxyphenyl)hex-2(E)-enoateC14H18O4Ee = >99%ee[α]D23=-12.9 (c 1.01, CHCl3)Source of chirality: stereoselective rearrangementAbsolute configuration: (4S,5S)(4S,5S)-Methyl 4-hydroxy-5-(4-methoxy-2-methylphenyl)hex-2(E)-enoateC15H20O4Ee = >99%ee[α]D20=-11.7 (c 1.40, CHCl3)Source of chirality: stereoselective rearrangementAbsolute configuration: (4S,5S)(4S,5S)-Methyl 4-hydroxy-5-(2-methoxy-4-methylphenyl)hex-2(E)-enoateC15H20O4Ee = >99%ee[α]D20=+25.1 (c 0.53, CHCl3)Source of chirality: stereoselective rearrangementAbsolute configuration: (4S,5S)(4S,5S)-Methyl 4-hydroxy-5-(4-methoxy-3-methylphenyl)hex-2(E)-enoateC15H20O4Ee = 99.3%ee[α]D21=-8.4 (c 1.00, CHCl3)Source of chirality: stereoselective rearrangementAbsolute configuration: (4S,5S)(4S,5S)-Methyl 4-hydroxy-5-(2,5-dimethoxyphenyl)hex-2(E)-enoateC15H20O4Ee = 98.2%ee[α]D21=0 (c 0.78, CHCl3)Source of chirality: stereoselective rearrangementAbsolute configuration: (4S,5S)(4S,5S)-Methyl 4-hydroxy-5-(3,4-dimethoxyphenyl)hex-2(E)-enoateC15H20O5Ee = 95.2%ee[α]D21=-4.1 (c 0.60, CHCl3)Source of chirality: stereoselective rearrangementAbsolute configuration: (4S,5S)(4S,5S)-Methyl 4-hydroxy-5-(2,5-dimethoxyphenyl)hex-2(E)-enoateC15H20O5Ee = 98.6%ee[α]D23=-12.1 (c 1.21, CHCl3)Source of chirality: stereoselective rearrangementAbsolute configuration: (4S,5S)(4S,5S)-Methyl 4-hydroxy-5-(2,5-dimethoxy-4-methylphenyl)hex-2(E)-enoateC16H22O5Ee = 99.8%ee[α]D23=-5.8 (c 1.22, CHCl3)Source of chirality: stereoselective rearrangementAbsolute configuration: (4S,5S)