Synlett, Table of Contents Synlett 2022; 33(01): 80-83DOI: 10.1055/s-0040-1719835 letter Enantioselective Synthesis of the Sex Pheromone of Lichen Moth, Miltochrista calamine, and Its Diastereomer Gucheng Yuan , Jiawei Liu , Shihang Yu , Xueyang Wang , Qinghua Bian , Min Wang , Jiangchun Zhong∗ Recommend Article Abstract Buy Article All articles of this category Abstract The synthesis of a Miltochrista calamine sex pheromone and its diastereomer has been developed. The key steps of the synthetic approach involved Evans’ chiral auxiliaries and the addition of alkyne to aldehyde, which were firstly applied to prepare this sex pheromone and its diastereomer. The synthetic sex pheromone could be used to trap insects and study physiological and ecological questions of the lichen moth. Key words Key words Miltochrista calamine - sex pheromone - asymmetric synthesis - Evans’ chiral auxiliary - alkynylation of aldehyde Full Text References References and Notes 1 Baker TC. Experientia 1989; 45: 248 2 Holdcraft R, Rodriguez-Saona C, Stelinski L. Insects 2016; 7: 17 3 Yang K, Wang C.-Z. Entomol. Exp. Appl. 2021; 169: 156 4 Kong W.-N, Wang Y, Guo Y.-F, Chai X.-H, Li J, Ma R.-Y. Pest Manage. Sci. 2020; 76: 3225 5 Yamakawa R, Kiyota R, Taguri T, Ando T. Tetrahedron Lett. 2011; 52: 5808 6 Do N D, Kinjo M, Taguri T, Adachi Y, Yamakawa R, Ando T. Biosci. Biotechnol. Biochem. 2009; 73: 1618 7 Adachi Y, Do ND, Kinjo M, Makisako S, Yamakawa R, Mori K, Ando T. J. Chem. Ecol. 2010; 36: 814 8 Luo Z, Cai X, Li Z, Bian L, Xin Z, Hussain F, Chen Z. J. Econ. Entomol. 2019; 112: 665 9 Fujii T, Yamakawa R, Terashima Y, Imura S, Ishigaki K, Kinjo M, Ando T. J. Chem. Ecol. 2013; 39: 28 10 Muraki Y, Taguri T, Yamakawa R, Ando T. J. Chem. Ecol. 2014; 40: 250 11a Ebner C, Pfaltz A. Tetrahedron 2011; 67: 10287 11b Yang JW, Hechavarria Fonseca MT, Vignola N, List B. Angew. Chem. Int. Ed. 2005; 44: 108 11c Palais L, Babel L, Quintard A, Belot S, Alexakis A. Org. Lett. 2010; 12: 1988 11d Heravi MM, Zadsirjan V, Farajpour B. RSC Adv. 2016; 6: 30498 11e Diaz-Munoz G, Miranda IL, Sartori SK, de Rezende DC, Alves Nogueira Diaz M. Chirality 2019; 31: 776 11f Tachihara T, Ishizaki S, Kurobayashi Y, Tamura H, Ikemoto Y, Onuma A, Kitahara T. Flavour Fragrance J. 2003; 18: 305 12 Fuwa H, Nakajima M, Shi J, Takeda Y, Saito T, Sasaki M. Org. Lett. 2011; 13: 1106 13 Tsakos M, Clement LL, Schaffert ES, Olsen FN, Rupiani S, Djurhuus R, Yu W, Jacobsen KM, Villadsen NL, Poulsen TB. Angew. Chem. Int. Ed. 2016; 55: 1030 14 Evans DA, Ennis MD, Mathre DJ. J. Am. Chem. Soc. 1982; 104: 1737 15 Wang Z, Xu Q, Tian W, Pan X. Tetrahedron Lett. 2007; 48: 7549 16 Eguchi T, Arakawa K, Terachi T, Kakinuma K. J. Org. Chem. 1997; 62: 1924 17 Dale JA, Dull DL, Mosher HS. J. Org. Chem. 1969; 34: 2543 18 Grisenti P, Ferraboschi P, Casati S, Santaniello E. Tetrahedron: Asymmetry 1993; 4: 997 19 Al Dulayymi JR, Baird MS, Roberts E. Tetrahedron 2005; 61: 11939 20 Barrett AG. M, Head J, Smith ML, Stock NS, White AJ. P, Williams DJ. J. Org. Chem. 1999; 64: 6005 21 Li N.-S, Scharf L, Adams EJ, Piccirilli JA. J. Org. Chem. 2013; 78: 5970 22 Newton S, Carter CF, Pearson CM, Alves LC, Lange H, Thansandote P, Ley SV. Angew. Chem. Int. Ed. 2014; 53: 4915 23 Experimental Procedures and Characterization Data for 12a,b In a 50 mL Schlenk tube, n-decyne (0.59 g, 4.28 mmol) and dry THF (20 mL) were added at room temperature under an argon atmosphere. After being cooled to –78 °C, n-butyllithium (1.34 mL, 2.4 M in THF, 3.21 mmol) was then added over 15 min via syringe pump. The resulting mixture was stirred for 0.5 h at –78 °C, followed by addition of aldehyde 11 (0.27 g, 2.14 mmol). The reaction was maintained for 0.5 h at –78 °C and quenched with saturated NH4Cl solution (10 mL). The organic phase was separated, and the aqueous phase was extracted with EtOAc (3 × 10 mL). The combined organic phases were washed with saturated NaCl solution (100 mL), dried over anhydrous Na2SO4, and filtered. The filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane/EtOAc, 9:1) to obtain 12a (0.28 g) and 12b (0.20 g) as a colorless oil (total 0.48 g, 84% yield, 12a/12b = 1.4:1, determined by 13C NMR). Compound 12a: [α]D 26 –5.64 (c 0.78, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 4.42 (t, J = 7.2 Hz, 1 H), 2.20 (td, J = 7.1, 1.8 Hz, 2 H), 1.75–1.66 (m, 3 H), 1.55–1.46 (m, 3 H), 1.44–1.10 (m, 16 H), 0.93–0.87 (m, 9 H). 13C NMR (126 MHz, CDCl3): δ = 85.49, 81.88, 61.10, 45.87, 36.78, 31.98, 29.84, 29.39, 29.33, 29.23, 29.16, 28.99, 28.81, 23.06, 22.80, 19.63, 18.82, 14.25. HRMS (ESI): m/z calcd for C18H35O [M + H]+: 267.26824; found: 267.26822. Compound 12b: [α]D 26 +1.67 (c 0.96, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 4.41 (t, J = 6.6 Hz, 1 H), 2.20 (td, J = 7.1, 1.9 Hz, 2H ), 1.70–1.62 (m, 3 H), 1.54–1.46 (m, 3 H), 1.37–1.13 (m, 16 H), 0.93–0.87 (m, 9 H). 13C NMR (126 MHz, CDCl3): δ = 85.81, 81.54, 61.64, 45.71, 36.88, 31.98, 29.83, 29.35, 29.24, 29.18, 28.98, 28.81, 23.06, 22.80, 19.85, 18.83, 14.27, 14.24. HRMS (ESI): m/z calcd for C18H35O [M + H]+: 267.26824; found: 267.26840 24 Pecunioso A, Maffeis M, Marchioro C. Tetrahedron: Asymmetry 1998; 9: 2787 25 Harit VK, Ramesh NG. J. Org. Chem. 2016; 81: 11574 26 Ohtani I, Kusumi T, Kashman Y, Kakisawa H. J. Am. Chem. Soc. 1991; 113: 4092 27 Gomez-Bengoa E, Garcia JM, Jimenez S, Lapuerta I, Mielgo A, Odriozola JM, Otazo I, Razkin J, Urruzuno I, Vera S, Oiarbide M, Palomo C. Chem. Sci. 2013; 4: 3198 28 The Experimental Procedures and Characterization Data for 1a,b In a 50 mL Schlenk tube, 10% palladium on carbon (0.10 g) was added at room temperature. The flask was charged with hydrogen, and 12a (82.3 mg, 0.31 mmol) in anhydrous ethanol (15 mL) and acetic acid (3 drops) were then added. The reaction mixture was stirred for 8 h under a hydrogen balloon. The catalyst was removed by filtering through a silica gel pad, and the filter was rinsed with n-hexane (30 mL). The combined filtrate and rinse were concentrated under a reduced pressure to obtain crude product. The crude product was purified by silica gel chromatography (n-hexane) to obtain 1a (77.7 mg, 93% yield) as a colorless oil. [α]D 26 –2.61 (c 1.38, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 3.68 (ddt, J = 12.2, 5.4, 3.4 Hz, 1 H), 1.62 (ddt, J = 12.2, 6.5, 2.5 Hz, 1 H), 1.44–1.40 (m, 4 H), 1.30–1.25 (m, 22 H), 1.17–1.15 (m, 1 H), 0.90–0.86 (m, 9 H). 13C NMR (126 MHz, CDCl3): δ = 69.84, 45.18, 38.54, 37.76, 32.06, 29.86, 29.79, 29.77 (×2), 29.48, 29.43, 29.36, 25.84, 23.12, 22.84, 19.45, 14.28, 14.26. HRMS (ESI): m/z calcd for C18H38ONa [M + Na]+: 293.28149; found: 293.28293. Following the similar procedure of 1a, the hydrogenation of 12b (92.8 mg, 0.35 mmol) afforded 1b (85.7 mg, 91% yield) as a colorless oil. [α]D 26 +0.73 (c 1.65, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 3.69 (tdd, J = 8.5, 4.9, 3.4 Hz, 1 H), 1.60–1.56 (m, 1 H), 1.43–1.38 (m, 4 H), 1.37–1.26 (m, 22 H), 1.12–1.05 (m, 1 H), 0.91–0.87 (m, 9 H). 13C NMR (126 MHz, CDCl3): δ = 70.20, 45.45, 37.95, 36.45, 32.06, 29.87, 29.84, 29.80, 29.77, 29.74, 29.49, 29.24, 25.71, 23.18, 22.84, 20.56, 14.29, 14.26. HRMS (ESI): m/z calcd for C18H38ONa [M + Na]+: 293.28149; found: 293.28244 Supplementary Material Supplementary Material Supporting Information
