(S)-2-methylbutanoic acid → (R)-2-Isopropenyl-5-methylhex-4-enyl (S)-2-methylbutanoate

HRID 558013Notes

Reaction equation

HRID 558013 reaction equation
CC(C)=CC[C@H](C(C)=C)CO.C[C@@H](CC)C(O)=O.[CH3:19][C@@H:20]([CH2:34][CH3:35])[C:21]([O:23][CH2:24][C@@H:25]1[CH2:28][C:27](=[C:29]([CH3:31])[CH3:30])[C:26]1([CH3:33])[CH3:32])=[O:22]>CO>[CH3:19][C@@H:20]([CH2:34][CH3:35])[C:21]([O:23][CH2:24][C@@H:25]([C:26]([CH3:33])=[CH2:32])[CH2:28][CH:27]=[C:29]([CH3:30])[CH3:31])=[O:22]

Participants

5

Reactant 3

HCID 448893(S)-2-methylbutanoic acidHCID 5464156(-)-LavandulolHCID 11299404[(R)-2,2-Dimethyl-3-(1-methylethylidene)cyclobutyl]methyl (S)-2-methylbutanoate

Product 1

HCID 71816609(R)-2-Isopropenyl-5-methylhex-4-enyl (S)-2-methylbutanoateYield 75%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Esterification of (R)-(−)-lavandulol {(86% ee, [α]24D−9.6 (c 0.1, MeOH), prepared according to the method described by Cardillo et al. (Cardillo, G., et al., J. Org. Chem., 53: 2354-2356 (1988))} with (S)-(+)-2-methylbutanoic acid using the same procedures as compound 2a gave 75 mg (75% yield) of 1a as clear oil. Optical purity: 99% ee; [α]24D+5.0 (c 0.1, MeOH); 1H NMR (C6D6): δ 0.83 (3H, t, J=7.29 Hz), 1.08 (3H, d, J=7.0 Hz), 1.35 (1H, m), 1.50 (3H, s), 1.59 (3H, t, J=0.80 Hz), 1.61 (3H, d, J=1.13 Hz), 1.68 (1H, m), 2.06 (2H, m), 2.28 (1H, sextet, 6.85 Hz), 2.42 (1H, quintet, 7.00 Hz), 4.12 (2H, m), 4.79 (1H, m), 4.83 (1H, quintet, J=1.51 Hz), 5.11 (1H, t, quintet, J=7.19, 1.52 Hz); 13C NMR (C6D6): δ 175.88, 146.31, 132.70, 122.00, 112.50, 66.68, 45.41, 41.22, 29.13, 26.00, 25.80, 20.00, 17.80, 16.50, 11.52; EI-MS m/z (%): 238 [M]+ (1), 169 (2), 156 (3), 136 (15), 121 (39), 107 (11), 93 (100), 85 (23), 80 (25), 69 (75), 57 (59), 41 (40); HREIMS: obsd. 238.1934, calcd. for C15H16O2 (M+): 238.1933.

Sources & evidence

ORD record
ord-2b68e01d67c747ed81cbaedc4064e176
Source dataset
uspto-grants-2011_11
Patent number
US08062651B1

Reaction notes

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