Enantioselective Synthesis of the Sex Pheromone of Lichen Moth, Miltochrista calamine, and Its Diastereomer

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

Miltochrista calamine - sex pheromone - asymmetric synthesis - Evans’ chiral auxiliary - alkynylation of aldehyde

Publication History

Received: 24 July 2021

Accepted after revision: 24 August 2021

Article published online:
22 September 2021

• 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