Enantioselective Synthesis of α-Chiral Amides by Catalytic Hydrogenation with Iridium N,P-Complexes

Abstract

The catalytic asymmetric hydrogenation of olefins constitutes a powerful method for the preparation of chiral compounds. A series of prochiral unsaturated amides were efficiently reduced with high enantioselectivities by means of an iridium N,P-complex-catalyzed hydrogenation. Its application in the synthesis of fenpropidin and the possibility of using isomeric mixtures of starting materials are attractive features of the method.

Key words

amides - enantioselectivity - iridium catalysis - asymmetric catalysis - hydrogenation

Publikationsverlauf

Eingereicht: 30. Oktober 2022

Angenommen nach Revision: 30. November 2022

Artikel online veröffentlicht:
22. Dezember 2022

• References and Notes

• 1a Nazari A, Heravi MM, Zadsirjan V. J. Organomet. Chem. 2021; 932: 121629
• 1b Heravi MM, Zadsirjan V, Farajpour B. RSC Adv. 2016; 6: 30498
• 1c Diaz-Muñoz G, Miranda IL, Sartori SK, de Rezende DC, Nogueira Diaz MA. Chirality 2019; 31: 776
• 2 Oh B.-H. Expert Opin. Pharmacother. 2007; 8: 2839
• 3 Chirumamilla RR, Marchant R, Nigam P. J. Chem. Technol. Biotechnol. 2001; 76: 123
• 4 Gayke M, Narode H, Eppa G, Bhosale RS, Yadav JS. ACS Omega 2022; 7: 2486
• 5 Narczyk A, Mrozowicz M, Stecko S. Org. Biomol. Chem. 2019; 17: 2770
• 6a Lanigan RM, Karaluka V, Sabatini MT, Starkov P, Badland M, Boulton L, Sheppard TM. Chem. Commun. 2016; 52: 8846
• 6b Sabatini MT, Boulton LT, Sheppard TD. Sci. Adv. 2017; 3: e1701028
• 6c Sabatini MT, Karaluka V, Lanigan RM, Boulton LT, Badland M, Sheppard TD. Chem. Eur. J. 2018; 24: 7033
• 7a Evans DA, Bartroli J, Shih TL. J. Am. Chem. Soc. 1981; 103: 2127
• 7b Chouhan M, Sharma R, Nair VA. Org. Lett. 2012; 14: 5672
• 7c Zhang Z, Collum DB. J. Org. Chem. 2017; 82: 7595
• 8a De Rycke N, St Denis JD, Hughes JM. E, Rosadiuk KA, Gleason JL. Synlett 2014; 2802
• 8b Ye P, Liu X, Wang G, Liu L. Chin. Chem. Lett. 2021; 32: 1237
• 8c Tong X, Schneck F, Fu GC. J. Am. Chem. Soc. 2022; 144: 14856
• 9a Ohtsuka Y, Ikeno T, Yamada T. Tetrahedron: Asymmetry 2003; 14: 967
• 9b Liu Y, Mao Y, Hu Y, Gui J, Wang L, Wang W, Zhang S. Adv. Synth. Catal. 2019; 361: 1554
• 10a Cui X, Burgess K. Chem. Rev. 2005; 105: 3272
• 10b Roseblade SJ, Pfaltz A. Acc. Chem. Res. 2007; 40: 1402
• 10c Minnaard AJ, Feringa BL, Lefort L, de Vries JG. Acc. Chem. Res. 2007; 40: 1267
• 10d Verendel JJ, Pàmies O, Diéguez M, Andersson PG. Chem. Rev. 2014; 114: 2130
• 10e Cabré A, Verdaguer X, Riera A. Chem. Rev. 2022; 122: 269
• 10f Peters BB. C, Andersson PG. J. Am. Chem. Soc. 2022; 144: 16252
• 11a Chung JY. L, Zhao D, Hughes DL, McNamara JM, Grabowski EJ. J, Reider PJ. Tetrahedron Lett. 1995; 36: 7379
• 11b Li P, Hu X, Dong X.-Q, Zhang X. Chem. Commun. 2016; 52: 11677
• 11c Han Z, Li P, Zhang Z, Chen C, Wang Q, Dong X.-Q, Zhang X. ACS Catal. 2016; 6: 6214
• 11d Wen J, Jiang J, Zhang X. Org. Lett. 2016; 18: 4451
• 11e Huang Y, Li P, Dong X.-Q, Zhang X. Org. Biomol. Chem. 2018; 16: 8819
• 11f Yin C, Yang T, Pan Y, Wen J, Zhang X. Org. Lett. 2020; 22: 920
• 11g Yang J, Li X, You C, Li S, Guan Y.-Q, Lv H, Zhang X. Org. Biomol. Chem. 2020; 18: 856
• 11h Hu T, Lückemeier L, Daniliuc C, Glorius F. Angew. Chem. Int. Ed. 2021; 60: 23193
• 11i Greszler SN, Zhao G, Shelat B, Voight EA. Org. Lett. 2022; 24: 7305
• 12 Lu W.-J, Hou X.-L. Adv. Synth. Catal. 2009; 351: 1224
• 13 Shang J, Han Z, Li Y, Wang Z, Ding K. Chem. Commun. 2012; 48: 5172
• 14a Yue T.-Y, Nugent WA. J. Am. Chem. Soc. 2002; 124: 13692
• 14b Zhou J, Ogle JW, Fan Y, Banphavichit V, Burgess K. Chem. Eur. J. 2007; 13: 7162
• 14c Tian F, Yao D, Liu Y, Xie F, Zhang W. Adv. Synth. Catal. 2010; 352: 1841
• 14d Metallinos C, Van Belle L. J. Organomet. Chem. 2011; 696:  141
• 14e Liu Y, Yao D, Li K, Tian F, Xie F, Zhang W. Tetrahedron 2011; 67: 8445
• 14f Liu Y, Zhang W. Angew. Chem. Int. Ed. 2013; 52: 2203
• 14g Liu X, Han Z, Wang Z, Ding K. Angew. Chem. Int. Ed. 2014; 53: 1978
• 14h Liu Y, Gridnev ID, Zhang W. Angew. Chem. Int. Ed. 2014; 53: 1901
• 14i Margalef J, Caldentey X, Karlsson EA, Coll M, Mazuela J, Pàmies O, Diéguez M, Pericàs MA. Chem. Eur. J. 2014; 20: 12201
• 14j Li Q, Wan P, He Y, Zhou Y, Li L, Chen B, Duan K, Cao R, Zhou Z, Qiu L. Asian J. Org. Chem. 2014; 3:  774
• 14k Borràs C, Biosca M, Pàmies O, Diéguez M. Organometallics 2015; 34: 5321
• 14l Biosca M, Coll M, Lagarde F, Brémond E, Routaboul L, Manoury E, Pàmies O, Poli R, Diéguez M. Tetrahedron 2016; 72: 2623
• 14m Biosca M, Magre M, Coll M, Pàmies O, Diéguez M. Adv. Synth. Catal. 2017; 359: 2801
• 14n Xia J, Nie Y, Yang G, Liu Y, Gridnev ID, Zhang W. Chin. J. Chem. 2018; 36: 612
• 14o Biosca M, Magre M, Pàmies O, Diéguez M. ACS Catal. 2018; 8: 10316
• 14p Margalef J, Borràs C, Alegre S, Alberico E, Pàmies O, Diéguez M. ChemCatChem 2019; 11: 2142
• 14q Biosca M, Pàmies O, Diéguez M. J. Org. Chem. 2019; 84: 8259
• 14r Margalef J, Biosca M, de la Cruz-Sánches P, Caldentey X, Rodríguez-Escrich C, Pàmies O, Pericàs MA, Diéguez M. Adv. Synth. Catal. 2021; 363: 4561
• 14s Faiges J, Borràs C, Pastor IM, Pàmies O, Besora M, Diéguez M. Organometallics 2021; 40: 3424
• 14t Nie Y, Li J, Yan J, Yuan Q, Zhang W. Org. Lett. 2021; 23: 5373
• 14u Ye X.-Y, Liang Z.-Q, Jin C, Lang Q.-W, Chen G.-Q, Zhang X. Chem. Commun. 2021; 57: 195
• 14v Nie Y, Li J, Yuan Q, Zhang W. Chin. J. Chem. 2022; 40: 819
• 15 The five-membered cyclic analogue [(E)-3-benzylidenepyrrolidin-2-one] was found to be unreactive under these reaction conditions.
• 16 Massaro L, Zheng J, Margarita C, Andersson PG. Chem. Soc. Rev. 2020; 49: 2504
• 17a Yang J, Massaro L, Krajangsri S, Singh T, Su H, Silvi E, Ponra S, Eriksson L, Ahlquist MS. G, Andersson PG. J. Am. Chem. Soc. 2021; 143: 21594
• 17b Peters BB. C, Zheng J, Birke N, Singh T, Andersson PG. Nat. Commun. 2022; 13: 361
• 17c Yang J, Ponra S, Li X, Peters BB. C, Massaro L, Zhou T, Andersson PG. Chem. Sci. 2022; 13: 8590
• 18 Hao H.-Y, Lou S.-J, Wang S, Zhou K, Wu Q.-Z, Mao Y.-J, Xu Z.-Y, Xu D.-Q. Chem. Commun. 2021; 57: 8055
• 19 α,β-Unsaturated Amides 1; General Procedure The appropriate α,β-unsaturated carboxylic acid (10.0 mmol, 1.00 equiv) was refluxed in SOCl₂ (5 mL) for 1 h, after which excess SOCl₂ was evaporated in vacuo. The resulting acyl chloride was redissolved in anhydrous CH₂Cl₂ (20 mL), and the solution was cooled to 0 °C. The appropriate amine (20.0 mmol, 2.00 equiv) and Et₃N (5.60 mL, 40.0 mmol, 4.00 equiv) were added, and the mixture was stirred overnight at room temperature. Sat. aq NH₄Cl (20 mL) was then added to quench the reactants, and the mixture was extracted with Et₂O (3 × 20 mL). The combined organic phases were washed with brine (20 mL), dried (Na₂SO₄), and evaporated to dryness in vacuo to give the crude product. This was purified by column chromatography [silica gel, pentane–Et₂O (60:40)] to give the desired α,β-unsaturated amide. This was filtered over basic Al₂O₃, eluting with pentane–Et₂O (60:40), immediately before hydrogenation.
• 20 4-[(2E)-2-methyl-3-phenylprop-2-enoyl]morpholine (1b) Synthesized, by following the general procedure, from (2E)-2-methyl-3-phenylacrylic acid (0.81 g, 5.0 mmol), morpholine (0.87 mL, 10.0 mmol), and Et₃N (2.8 mL, 20.0 mmol) as a colorless oil; yield: 0.94 g (4.1 mmol, 82%). ¹H NMR (400 MHz, CDCl₃): δ = 7.41–7.27 (m, 5 H), 6.54 (q, J = 1.7 Hz, 1 H), 3.75–3.69 (m, 4 H), 3.66 (m, 4 H), 2.11 (d, J = 1.6 Hz, 3 H). The spectroscopic data were in agreement with the reported values.^23a
• 21 Asymmetric Hydrogenation of α,β-Unsaturated Amides An oven-dried vial was charged with the appropriate unsaturated amide (0.1 mmol, 1.0 equiv) and Ir-N,P catalyst (1.0 mol%). Freshly distilled toluene (0.5 mL) and a magnetic stirring bar were added, and the vial was placed in a high-pressure hydrogenation apparatus. The reactor was purged three times with Ar and three times with H₂, then pressurized with H₂ (10 bar). The mixture was stirred at rt for 16 h before the H₂ pressure was released and the solvent was removed under reduced pressure. The residue was purified by flash chromatography [silica gel, pentane–Et₂O (25:75)] to give the chiral alkane. The enantioselectivity was determined by GC or SFC analysis on a chiral stationary phase. The corresponding racemic product, used for comparison, was prepared on a 0.05 mmol scale by using Pd/C or a racemic Ir catalyst, following the same hydrogenation procedure. The absolute configuration was determined by comparing the sign of the optical rotation with the reported value.
• 22 4-(2-Methyl-3-phenylpropanoyl)morpholine (2b) Prepared, by following the general procedure, from 1b (23.1 mg, 0.1 mmol) in the presence of catalyst F as a colorless oil; yield: 23.1 mg (0.99 mmol, 99%); [α]_D ²⁶ +35.0 (c 0.1 M, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.32–7.24 (m, 3 H), 7.18–7.13 (m, 2 H), 3.74–3.54 (m, 2 H), 3.50–3.41 (m, 3 H), 3.35–3.25 (m, 1 H), 3.20–3.10 (m, 1 H), 3.05–3.00 (m, 1 H), 3.00–2.89 (m, 2 H), 2.75–2.64 (m, 1 H), 1.18 (d, J = 6.4 Hz, 3 H). The spectroscopic data were in agreement with the reported values.^23b
• 23a Hayashi C, Hayashi T, Yamada T. Bull. Chem. Soc. Jpn. 2015; 88: 862
• 23b Banerjee A, Hattori T, Yamamoto H. Synthesis 2023; in press