Acetic Anhydride–Acetic Acid as a New Dehydrating Agent of Aldoximes for the Preparation of Nitriles: Preparation of 2-Cyanoglycals

Tommy F. Mabasa; Jackie Mabasa; Mthokozisi Simelane; Banele Vatsha; Banothile C.E. Makhubela; Henok H. Kinfe

doi:10.1055/s-0040-1708007

Synlett, Table of Contents

Synlett 2020; 31(10): 991-996
DOI: 10.1055/s-0040-1708007

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Acetic Anhydride–Acetic Acid as a New Dehydrating Agent of Aldoximes for the Preparation of Nitriles: Preparation of 2-Cyanoglycals

Tommy F. Mabasa

^aCentre of Synthesis and Catalysis, University of Johannesburg, Auckland Park Campus, Auckland Park 2006, Johannesburg, South Africa

,

Jackie Mabasa

^aCentre of Synthesis and Catalysis, University of Johannesburg, Auckland Park Campus, Auckland Park 2006, Johannesburg, South Africa

,

Mthokozisi Simelane

^bDepartment of Biochemistry, University of Johannesburg, Auckland Park Campus, Auckland Park 2006, Johannesburg, South Africa Email: hhkinfe@uj.ac.za

,

Banele Vatsha

^aCentre of Synthesis and Catalysis, University of Johannesburg, Auckland Park Campus, Auckland Park 2006, Johannesburg, South Africa

,

Banothile C.E. Makhubela

^aCentre of Synthesis and Catalysis, University of Johannesburg, Auckland Park Campus, Auckland Park 2006, Johannesburg, South Africa

,

Henok H. Kinfe∗

^aCentre of Synthesis and Catalysis, University of Johannesburg, Auckland Park Campus, Auckland Park 2006, Johannesburg, South Africa

› Author Affiliations

Abstract

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Abstract

Glycals, 1,2-unsatrated carbohydrates, are versatile building blocks for the synthesis of various scaffolds. Despite their potential to serve as suitable precursors in diversity-oriented synthesis, 2-cyanoglycals are less explored in terms of their synthesis and derivatization. Herein, we report a combination of Ac₂O and AcOH as new and efficient dehydrating agent of aldoximes for the synthesis of 2-cyanoglycals. In comparison to the conventional dehydrating system of Ac₂O-base (such as NaOH, NaOAc and K₂CO₃), the current protocol provides superior yields and faster reaction rates. The scope and limitations of the dehydrating system are investigated.

Key words

aldoximes - 2-cyanoglycals - nitriles

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References

References and Notes
1 Yu H, Richey RN, Miller WD, Xu J, May SA. J. Org. Chem. 2011; 76: 665 ; and references cited therein.
2 Du B, Jiang X, Sun P. J. Org. Chem. 2013; 78: 2786
3 Dai H.-X, Li G, Zhang X.-G, Stepan AF, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 7567
4 Lee S, Lee H, Tan K. J. Am. Chem. Soc. 2013; 135: 18778
5 Tang R.-Y, Li G, Yu J.-Q. Nature 2014; 507: 215
6 Yang G, Lindovska P, Zhu D, Kim J, Wang P, Tang RY, Movassaghi M, Yu J.-Q. J. Am. Chem. Soc. 2014; 136: 10807
7 Bera M, Modak A, Patra T, Maji A, Maiti D. Org. Lett. 2014; 16: 5760
8 Deng Y, Yu I.-Q. Angew. Chem. Int. Ed. 2015; 54: 888
9 Bera M, Maji A, Sahoo SK, Maiti D. Angew. Chem. Int. Ed. 2015; 54: 8515
10 Li S, Ji H, Cai L, Li G. Chem. Sci. 2015; 6: 5595
11 Sandmeyer T. Ber. Dtsch. Chem. Ges. 1884; 17: 1633

12a Ushkov AV, Grushin VV. J. Am. Chem. Soc. 2011; 133: 10999
12b Yeung PY, So CM, Lau CP, Kwong FY. Org. Lett. 2011; 13: 648
12c Coombs JR, Fraunhoffer KJ, Simmons EM, Stevens JM, Wisniewski SR, Yu M. J. Org. Chem. 2017; 82: 7040
12d Cohen DT, Buchwald SL. Org. Lett. 2015; 17: 202
12e Zhang X, Xia A, Chen H, Liu Y. Org. Lett. 2017; 19: 2118
12f Tu Y, Zhang Y, Xu S, Zhang Z, Xie X. Synlett 2014; 25: 2938
12g Grossman O, Gelman D. Org. Lett. 2006; 8: 1189
12h Weissman SA, Zewge D, Chen C. J. Org. Chem. 2005; 70: 1508
12i Qi C, Hu X, He H. Synlett 2016; 27: 1979
12j Chatterjee T, Dey R, Ranu BC. J. Org. Chem. 2014; 79: 5875
12k Yu H, Richey RN, Miller WD, Xu J, May SA. J. Org. Chem. 2011; 76: 665
12l Littke A, Soumeillant M, Kaltenbach RF. III, Cherney RJ, Tarby CM, Kiau S. Org. Lett. 2007; 9: 1711
12m Zanon J, Klapars A, Buchwald SL. J. Am. Chem. Soc. 2003; 125: 2890
12n Cheng Y.-n, Duan Z, Li T, Wu Y. Synlett 2007; 543
12o Gan Y, Wang G, Xie X, Liu Y. J. Org. Chem. 2018; 83: 14036
12p Takise R, Itami K, Yamaguchi J. Org. Lett. 2016; 18: 4428
12q Heravi MM, Panahi F, Iranpoor N. Org. Lett. 2018; 20: 2753

13 Yang SH, Chang S. Org. Lett. 2001; 3: 4209
14 Li D, Shi F, Guo S, Deng Y. Tetrahedron Lett. 2005; 46: 671
15 Yadav LD. S, Srivastava VP, Patel R. Tetrahedron Lett. 2009; 50: 5532
16 Kim HS, Kim SH, Kim JN. Tetrahedron Lett. 2009; 50: 1717
17 Enthaler S, Weidauer M, Schröder F. Tetrahedron Lett. 2012; 53: 882
18 Ma X.-Y, He Y, Lu T.-T, Lu M. Tetrahedron 2013; 69: 2560
19 Ghosh P, Subba R. Tetrahedron Lett. 2013; 54: 4885
20 Ghosh P, Saha B, Pariyar GC, Tamang A, Subba R. Tetrahedron Lett. 2016; 57: 3618
21 Leggio A, Belsito EL, Gallo S, Liguori A. Tetrahedron Lett. 2017; 58: 1512

22a Hauser CR, Jordan E. J. Am. Chem. Soc. 1935; 57: 2450
22b Mowry DT, Morner RR. J. Am. Chem. Soc. 1947; 69: 1831
22c Browne MF, Shriner RL. J. Org. Chem. 1957; 22: 1320
22d Anderson HJ. Can. J. Chem. 1959; 37: 2053
22e Anderson HJ. Can. J. Chem. 1968; 46: 798
22f Song Y, Shen D, Zhang Q, Chen B, Xu G. Tetrahedron Lett. 2014; 55: 639

23 Moshapo PT, Mokela S, Mmutlane EM, Mampa RM, Kinfe HH. Org. Biomol. Chem. 2016; 14: 5627
24 Kinfe HH. Org. Biomol. Chem. 2019; 17: 4153
25 Malinowski M, Tran TV, de Robichon M, Lubin-Germain N, Ferry A. Adv. Synth. Catal. 2020; 362: 1
26 Hall RH, Jordaan A. J. Chem. Soc., Perkin Trans. 1 1973; 1059
27 CCDC 1969200 (2d) and 1969201 (3) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
28 Typical procedure: A solution of pre-prepared aldoxime 1a (100 mg, 0.218 mmol) in AcOH/Ac₂O (1:1.75, 2 mL) in a 10 mL round-bottom flask fitted with a condenser was heated at 110 °C for 4 h under a nitrogen atmosphere. The reaction mixture was then allowed to cool to room temperature and 15% aq. NaOH was added until the solution became slightly basic. The resultant mixture was extracted with ethyl acetate and the combined organic phases were washed successively with saturated bicarbonate, brine and water, dried over MgSO₄ and concentrated to dryness. The residue product was purified by column chromatography on silica gel using a mixture of ethyl acetate/hexane (9:1) as eluent to provide 2-cyanoglucal 2a in 72% yield. Compound 2a: Yield: 72%; colorless oil. IR (neat): 2214.3 cm^–1 (C≡N). HRMS: m/z [M + Na]⁺ calcd: 441.1940; found: 441.1835. ¹H NMR (CDCl₃, 400 MHz): δ = 7.40–7.23 (m, 15 H, Ar), 7.15 (s, 1 H, H1), 4.78 (d, J = 11.5 Hz, 1 H, -CH _1aPh), 4.70–4.55 (m, 3 H, -CH ₂Ph and -CH _1bPh), 4.50 (s, 2 H, -CH ₂Ph), 4.39 (q, J = 14.8 Hz, 1 H, H5), 4.14 (d, J = 4.8 Hz, 1 H, H3), 3.86 (t, J = 10.4 Hz, 1 H, H4), 3.77 (dd, J = 6.0, 11.0 Hz, 1 H, H6_a), 3.68 (dd, J = 3.5, 14.5 Hz, 1 H, H6_b). ¹³C NMR (100 MHz, CDCl₃): δ = 157.0 (C1), 137.5, 137.2, 137.1, 128.6, 128.5, 128.4, 128.2, 128.1, 128.06, 128.0, 127.9, 127.8, 127.7 (Ar), 117.9 (C2), 89.1 (CCN), 77.9 (C5), 73.5, 73.1, 72.6 (CH₂Ph×3), 71.9 (C3 and C4), 67.5 (C6).
29 Booma C, Balasubramanian KK. J. Chem. Soc., Perkin Trans. 1 1993; 393

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