TY - JOUR
T1 - Biochemical preparations of both the enantiomers of methyl 3-hydroxypentanoate and their conversion to the enantiomers of 4-hexanolide, the pheromone of trogoderma glabrum1 1 This paper forms part 6 of the series. Preparative Bioorganic Chemistry, Part 5, T. Sugai and K. Mori, Agric. Biol. Chem. 48,2501 (1984).
AU - Mori, Kenji
AU - Mori, Hideto
AU - Sugai, Takeshi
N1 - Funding Information:
(a) (S)-Isomer. NaOH (4.62 g, 115.5 mmol) in water (14 ml) was added to a soln of Q-8 (5.74 g, 29.0 mmol) in 2-methoxyethanol(40 ml). The mixture was stirred and heated under reflux for 21 hr. After acidi6cation with 3N HCl to pH 2, the mixture was extracted with ether. The aq layer was saturated with NaCl and further extracted with ether. The ether soln was dried (MgS03 and concentrated to give 4 g of a crude oil. This was dissolved in MeGH (15 ml) and made alkaline with KOH soln (965 mg in 20 ml water). The mixture was stirred for 4.5 hr at room temp, evaporated in uacuo to remove MeOH and extracted with ether to remove neutral impurities. The aq layer was acidified with 3 N HCl to pH 2 and stirred for 1 hr at room temp. It was then extracted with ether. The ether soln was dried (MgSO,) and concentrated in vacua to give 1.7 g of crude Q-3. This was distilled to give 1.3345 g (40.3%) of (.9)-J, b.p. 102-R&“/23 mm, ng”.’ 1.4325; [a];‘.’ -50.6” (c = 1.485, MeGH) ; v, 2980 (m), 2950(m), 2890(m), 1775 (s), 1460 (m), 1420 (w), 1385 (s), 1355 (m), 1285 (w), 1220 (m), 1185 (s), 1175 (s), 1130 (m), 1120 (m), 1100 (m), 1070 (w), 1055(w),1025(m),1015(m),970(m),955(m),9CUl(m),85O(w), 805(w),775(w)cm-‘;6(CC1~)1.00(3H,t,J = 7H$,i.4$2.67 (6H.m).4.1O-4.54(1H.m):GLC(column.1O’?~PEG-20M.2m -x4 km; carriei gai, ‘i&; 1 kg/cmz;’ co&m temp iooo + 10”/min) : Rt 7 min 57 set (looO/,).( Found : C, 62.74; H, 8.81. Calc for C,H,,O,: C, 63.13; H, 8.83x.) (b)(R~Jsomer. In thesamemanner asabove(R)-l#(2.0& 10.1 mmol) yielded 897.3 mg (77.5%) of (R)-3, b.p. 113”/32 mm, ni’ 1.4326; [a];’ + 53.1” (c = 1.005, MeOH). The IR and NMR spectra were identical with those of (S)-3. GLC (column, 5% PEG-20M, 2m x 4 mm ; carrier gas, N2 ; 1 kg/cm’ ; column temp loo” + 10”/min): Rt 4 min 18 set (99.3%). (Found: C, 63.00; H, 9.06. Calcfor C,H,,O,: C, 63.13; H, 8.83x.) Determination of the optical purity of 3 (R)- or Q-3 (100 mg, 0.876 mmol) was treated with 5 eq of MeMgI to give 100 mg (78.1%) of (R)-!Ia or 120 mg (93.7%) of (S)-9a, respectively. ‘H-NMR measurements at 100 MHz (Jeol FX-100). (i)(R)-9a(4.3mg)+Eu(tfc),(21mg,0.8eq)inCC1,(0.3ml)andCDCl3 (0.12 ml): S 3.82 (3H, s), 4.55 (3H, s); (ii) (S)-9a (5.1 mg) + Eu(ffc), (24.9 mg, 0.8 eq) in CCl, (0.3 ml) and CDCl, (0.12 ml) : 8 4:25’( 3H, ~1-5.02 (3H, s) ; (ibj ( f )-5%u nder the same condition : 6 4.27.4.33.5.10.5.22. The ootical uuritv of (RMa and that o(fS )-!htw ere therefore >95%. - _ . ’ HPLC analysis of9b. (R)- or (S)-9a was converted to the corresponding (S)-MTPA ester (R)- or (S)-9b in the usual manner” and they were analysed by HPLC (column, Partisil 5,25 cm x 4.6 mm; solvent, n-hexaneTHF (10: 1); flow rate 0.78 ml/min ; press, 37 kg/cm2 ; detection at 254 nm). The two diastereomers showed Rt 46 min 9 set and 48 min 4 set, respectively. (R)-9b was shown to be 100% pure. (S)-9b showed two peaks (97.45:2.55). The optical purity of (R)-3 was therefore loo”/, and that of (S)-3 was 95%. This was in almost complete agreement with the values estimated from the comparison of the [a]o values of our samples with that ( f 53.29 reported by Ravid et al.14 Acknowledgements-Our thanks are due to the following scientists for their gifts of materials : Dr. A. Echigo, Oriental Yeast Co. Ltd. (baker’s yeast), Mr. A. Shimosaka, Kirin Brewery Co. Ltd. (other yeasts) and Dr. J. Hasegawa, Kanegatuchi Chemical Industry Co. Ltd. (methyl (R)-3-hydroxypentanoate). This work was supported by a grant-in-aid for scientific research from the Japanese Ministry of Education, Science and Culture.
PY - 1985
Y1 - 1985
N2 - Title full: Biochemical preparations of both the enantiomers of methyl 3-hydroxypentanoate and their conversion to the enantiomers of 4-hexanolide, the pheromone of trogoderma glabrum1 1 This paper forms part 6 of the series. Preparative Bioorganic Chemistry, Part 5, T. Sugai and K. Mori, Agric. Biol. Chem. 48,2501 (1984). The experimental part of this work was taken from the B.Sc. Thesis of H.M. (March, 1984). This work was presented as a part of K.M.'s lecture at the Second Japan-Korea Seminar on Organic Chemistry (Kyoto, May 30,1984). Both the enantiomers of methyl 3-hydroxypentanoate were prepared by microbial asymmetric reduction of 3-oxopentanoic esters. Conversion of methyl 3-hydroxypentanoate to 4-hexanolide, the pheromone of Trogoderma glabrum, was achieved.
AB - Title full: Biochemical preparations of both the enantiomers of methyl 3-hydroxypentanoate and their conversion to the enantiomers of 4-hexanolide, the pheromone of trogoderma glabrum1 1 This paper forms part 6 of the series. Preparative Bioorganic Chemistry, Part 5, T. Sugai and K. Mori, Agric. Biol. Chem. 48,2501 (1984). The experimental part of this work was taken from the B.Sc. Thesis of H.M. (March, 1984). This work was presented as a part of K.M.'s lecture at the Second Japan-Korea Seminar on Organic Chemistry (Kyoto, May 30,1984). Both the enantiomers of methyl 3-hydroxypentanoate were prepared by microbial asymmetric reduction of 3-oxopentanoic esters. Conversion of methyl 3-hydroxypentanoate to 4-hexanolide, the pheromone of Trogoderma glabrum, was achieved.
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U2 - 10.1016/S0040-4020(01)96410-5
DO - 10.1016/S0040-4020(01)96410-5
M3 - Article
AN - SCOPUS:33749135890
SN - 0040-4020
VL - 41
SP - 919
EP - 925
JO - Tetrahedron
JF - Tetrahedron
IS - 5
ER -