Simple Synthesis of Dimethyl Nitrobenzhydrylphosphonates and Heteroarylnitroarylacetonitriles via Vicarious Nucleophilic Substitution (VNS) Reaction

Mieczysław Mąkosza; Małgorzata Bechcicka; Krzysztof Wojciechowski

doi:10.1055/s-0040-1707230

Synthesis, Inhaltsverzeichnis

Synthesis 2021; 53(01): 175-181
DOI: 10.1055/s-0040-1707230

paper

Simple Synthesis of Dimethyl Nitrobenzhydrylphosphonates and Heteroarylnitroarylacetonitriles via Vicarious Nucleophilic Substitution (VNS) Reaction

Mieczysław Mąkosza∗

Institute of Organic Chemistry Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warszawa, Poland eMail: icho-s@icho.edu.pl

,

Małgorzata Bechcicka

,

Krzysztof Wojciechowski

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Acetals of dimethyl phenyl- and heteroaryl-α-hydroxymethanephosphonates were deprotonated to generate carbanions, which enter the vicarious nucleophilic substitution (VNS) of hydrogen in aromatic nitro compounds to form 4-nitrobenzhydrylphosphonates and α-heteroaryl-4-nitrobenzylphosphonates. Similarly acetals of cyanohydrins of heteroaromatic aldehydes (furfural and 2-formylthiophene) react to form heteroaryl 4-nitroarylacetonitriles. The anion of the hemiacetal of acetaldehyde is an efficient leaving group in the base-induced β-elimination step – the crucial step in the VNS reaction. The reaction selectively occurred at the para-position to the nitro group.

Key words

arylmethanephosphonates - arylacetonitriles - carbanions - nitroarenes - acetals - vicarious nucleophilic substitution

Volltext

Referenzen

References

1a Goliński J, Mąkosza M. Tetrahedron Lett. 1978; 3495
1b Mąkosza M, Winiarski J. Acc. Chem. Res. 1987; 20: 282
1c Mąkosza M, Wojciechowski K. Chem. Rev. 2004; 104: 2631
1d Mąkosza M. Chem. Soc. Rev. 2010; 39: 2855
1e Mąkosza M. Synthesis 2017; 49: 3247
1f Loska R., Mąkosza M.; Synthesis 2020, 52: in press; DOI: 10.1055/s-0040-1707149.

2 Mąkosza M, Goliński J. Angew. Chem. Int. Ed. 1982; 21: 451

3a Mąkosza M, Goliński J, Baran J. J. Org. Chem. 1984; 49: 1488
3b Brześkiewicz J, Loska R, Mąkosza M. J. Org. Chem. 2018; 83: 8499

4a Mąkosza M, Winiarski J. Chem. Lett. 1984; 13: 1623
4b Mąkosza M, Danikiewicz W, Wojciechowski K. Liebigs Ann. Chem. 1988; 203

5 Mąkosza M, Winiarski J. J. Org. Chem. 1984; 49: 1494

6a Engel R. Chem. Rev. 1977; 77: 349
6b Moonen K, Laureyn I, Stevens CV. Chem. Rev. 2004; 104: 6177

7 Demmer CS, Krogsgaard-Larsen N, Bunch L. Chem. Rev. 2011; 111: 7981
8 Pallikonda G, Chakravarty M. Eur. J. Org. Chem. 2013; 944
9 Montel S, Raffier L, He YY, Walsh PJ. Org. Lett. 2014; 16: 1446

10a Lawrence NJ, Liddle J, Jackson DA. Tetrahedron Lett. 1995; 36: 8477
10b Harger MJ. P. J. Chem. Soc., Perkin Trans. 2 2001; 41

11a Mąkosza M, Sulikowski D. Synlett 2010; 1666
11b Mąkosza M, Sulikowski D. J. Org. Chem. 2009; 74: 3827

12 Prasad SS, Singh DK, Kim I. J. Org. Chem. 2019; 84: 6323

13a Sisido K, Nozaki H, Nozaki M, Okano K. J. Org. Chem. 1954; 19: 1699
13b Sumi T, Goseki R, Otsuka H. Chem. Commun. 2017; 53: 11885

14a Chen G, Wang Z, Wu J, Ding KL. Org. Lett. 2008; 10: 4573
14b Theerthagiri P, Lalitha A. Tetrahedron Lett. 2012; 53: 5535

15 Nambo M, Yar M, Smith JD, Crudden CM. Org. Lett. 2015; 17: 50
16 Mąkosza M, Jagusztyn-Grochowska M, Ludwikow M, Jawdosiuk M. Tetrahedron 1974; 30: 3723

17a Hermann CK. F, Sachdeva YP, Wolfe JF. J. Heterocycl. Chem. 1987; 24: 1061
17b Cherng Y.-J. Tetrahedron 2002; 58: 4931

18 Yin Z, Zhang Z, Kadow JF, Meanwell NA, Wang T. J. Org. Chem. 2004; 69: 1364
19 Temelli B, Unaleroglu C. Synthesis 2014; 46: 1407
20 Rad N, Mąkosza M. Eur. J. Org. Chem. 2018; 376
21 Kozlowski JK, Rath NP, Spilling CD. Tetrahedron 1995; 51: 6385
22 Mąkosza M, Goetzen T. Org. Prep. Proced. Int. 1973; 5: 203
23 Singh DK, Prasad SS, Kim J, Kim I. Org. Chem. Front. 2019; 6: 669

Zusatzmaterial

Supporting Information