Efficient Syntheses of Diverse N-Heterocycles: The Molybdenum(VI)-Catalyzed Reductive Cyclization of Nitroarenes using Pinacol as a Deoxygenating­ Agent

Raghuram Gujjarappa; Nagaraju Vodnala; Arup K. Kabi; Dhananjaya Kaldhi; Mohan Kumar; Uwe Beifuss; Chandi C. Malakar

doi:10.1055/s-0036-1591572

SynOpen, Table of Contents

CC BY ND NC 4.0 · SynOpen 2018; 02(02): 0138-0144
DOI: 10.1055/s-0036-1591572

paper

Copyright with the author

Efficient Syntheses of Diverse N-Heterocycles: The Molybdenum(VI)-Catalyzed Reductive Cyclization of Nitroarenes using Pinacol as a Deoxygenating Agent

Raghuram Gujjarappa

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal-795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Nagaraju Vodnala

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal-795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Arup K. Kabi

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal-795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Dhananjaya Kaldhi

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal-795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Mohan Kumar

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal-795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Uwe Beifuss

^bInstitut für Chemie, Universität Hohenheim, Garbenstr. 30, 70599 Stuttgart, Germany

,

Chandi C. Malakar *

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal-795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

› Author Affiliations

Abstract

All articles of this category

Abstract

Molybdenum(VI)-catalyzed domino reductive cyclization of nitroarenes has been devised for the syntheses of 1,4-benzoxazines and 1,4-benzothiazines in the presence of pinacol as deoxygenating agent. The scope of the described method was further extended to the syntheses of the rarely explored scaffolds, 1-hydroxyphenazines and quinoxalines. The present method avoids the use of hazardous deoxygenating agents and operates under solvent-free conditions.

Key words

N-heterocycles - domino reaction - reductive cyclization - nitroarenes - dioxo-Mo(VI) complex - pinacol

Full Text

References

References

1a Royer J. Asymmetric Synthesis of Nitrogen Heterocycles . Wiley-VCH Verlag; Weinheim: 2009
1b Huang Y. Khoury K. Dömling A. In Synthesis of Heterocycles via Multicomponent Reactions I . Vol. 23. Orru RV. A. Ruijter E. Springer; Berlin, Heidelberg: 2010: p 85
1c Wolfe JP. Neukom JD. Mai DH. Synthesis of Saturated Five-Membered Nitrogen Heterocycles via Pd-Catalyzed C–N Bond-Forming Reactions. Wiley-VCH Verlag; Weinheim: 2011
1d Eicher T. Hauptmann S. Speicher A. Chemistry of Heterocycles: Structure, Reactions, Synthesis, and Applications . Wiley; Somerset, NJ: 2013
1e Wolfe JP. Synthesis of Heterocycles via Metal-Catalyzed Reactions That Generate One or More Carbon–Heteroatom Bonds. Springer; Berlin, Heidelberg: 2013
1f Sammes PG. Chem. Rev. 1976; 76: 113
1g Fodor L. Szabó J. Bernáth G. Sohár P. Maclean DB. Smith RW. Ninomiya I. Naito T. J. Heterocycl. Chem. 1989; 26: 333
1h Diurno MV. Mazzoni O. Izzo AA. Bolognese A. Farmaco 1997; 52: 257
1i Cecchetti V. Filipponi E. Fravolini A. Tabarrini O. Xin T. Bioorg. Med. Chem. 1997; 5: 1339
1j Deziel R. Malenfant E. Bioorg. Med. Chem. Lett. 1998; 8: 1437
1k Armenise D. Trapani G. Stasi F. Morlacchi F. Arch. Pharm. 1998; 331: 54
1l Feher M. Schmidt JM. J. Chem. Inf. Comput. Sci. 2002; 43: 218
1m Hilton ST. Motherwell WB. Potier P. Pradet C. Selwood DL. Bioorg. Med. Chem. Lett. 2005; 15: 2239
1n Song Z.-C. Ma G.-Y. Lv PC. Li HQ. Xiao ZP. Zhu HL. Eur. J. Med. Chem. 2009; 44: 3903
1o Gomez- MonterreyI. Bertamino A. Porta A. Carotenuto A. Musella S. Aquino C. Granata I. Sala M. Brancaccio D. Picone D. Ercole C. Stiuso P. Campiglia P. Grieco P. Ianelli P. Maresca B. Novellino E. J. Med. Chem. 2010; 53: 8319
1p Kaur SP. Rao R. Nanda S. Int. J. Pharm. 2010; 402: 37
1q Leeson PD. St-Gallay SA. Wenlock MC. MedChemComm 2011; 2: 91
1r Kaur SP. Rao R. Nanda S. Int. J. Pharm. Pharm. Sci. 2011; 3: 30
1s Jarvis CL. Richers MT. Breugst M. Houk KN. Seidel D. Org. Lett. 2014; 16: 3556
1t Feng H. Jia H. Sun Z. Adv. Synth. Catal. 2015; 357: 2447

2a Lovering F. Bikker J. Humblet C. J. Med. Chem. 2009; 52: 6752
2b Schnurch M. Dastbaravardeh N. Ghobrial M. Mrozek BD. Mihovilovic M. Curr. Org. Chem. 2011; 15: 2694
2c Ritchie TJ. Macdonald SJ. F. Young RJ. Pickett SD. Drug Discovery Today 2011; 16: 164
2d Zhu Z. Tang X. Li J. Li X. Wu W. Deng G. Jiang H. Org. Lett. 2017; 19: 1370
2e Song P. Yu P. Lin J.-S. Li Y. Yang N.-Y. Liu X.-Y. Org. Lett. 2017; 19: 1330
2f Yan F. Liang H. Song J. Cui J. Liu Q. Liu S. Wang P. Dong Y. Liu H. Org. Lett. 2017; 19: 86

3a Colby DA. Bergman RG. Ellman JA. Chem. Rev. 2010; 110: 624
3b Engle KM. Mei TS. Wasa M. Yu J.-Q. Acc. Chem. Res. 2011; 45: 788
3c Lu P. Wang Y. Chem. Soc. Rev. 2012; 41: 5687
3d El-salam NM. A. Mostafa MS. Ahmed GA. Alothman OY. J. Chem. 2013; 1
3e Azab ME. Youssef MM. El-Bordany EA. Molecules 2013; 18: 832
3f Salem MS. Sakr SI. El-Senousy WM. Madkour HM. F. Arch. Pharm. (Weinheim) 2013; 346: 766
3g Xu X. Doyle MP. Acc. Chem. Res. 2014; 47: 1396
3h Xie J. Pan C. Abdukadera A. Zhu C. Chem. Soc. Rev. 2014; 43: 5245
3i Cao X. Sun Z. Cao Y. Wang R. Cai T. Chu W. Hu W. Yang Y. J. Med. Chem. 2014; 57: 3687
3j Chen Y. Yu K. Tan NY. Qiu RH. Liu W. Luo NL. Tong L. Au CT. Luo ZQ. Yin SF. Eur. J. Med. Chem. 2014; 79: 391
3k Sharma UK. Sharma N. Vachhani DD. der Eycken EV. V. Chem. Soc. Rev. 2015; 44: 1836
3l Yang L. Huang H. Chem. Rev. 2015; 115: 3468
3m Martins P. Jesus J. Santos S. Raposo LR. Roma-Rodrigues C. Baptista PV. Fernandes AR. Molecules 2015; 20: 16852
3n Yu J.-T. Pan C. Chem. Commun. 2016; 2220

4a Felpin F.-X. Lebreton J. Eur. J. Org. Chem. 2003; 3693
4b Ragaini F. Cenini S. Brignoli D. Gasperini M. Gallo E. J. Org. Chem. 2003; 68: 460
4c Smitrovich JH. Davies IW. Org. Lett. 2004; 6: 533
4d Pyne SG. Davis AS. Gates NJ. Hartley JP. Lindsay KB. Machan T. Tang M. Synlett 2004; 2670
4e Coldham I. Hufton R. Chem. Rev. 2005; 105: 2765
4f Bellina F. Rossi R. Tetrahedron 2006; 62: 7213
4g Merisor E. Conrad J. Klaiber I. Mika S. Beifuss U. Angew. Chem. Int. Ed. 2007; 46: 3353
4h Merisor E. Conrad J. Mika S. Beifuss U. Synlett 2007; 2033
4i Merisor E. Beifuss U. Tetrahedron Lett. 2007; 48: 8383
4j Ferretti F. Formenti D. Ragaini F. Rend. Lincei 2017; 28: 97
4k El-Atawy MA. Ferretti F. Ragaini F. Eur. J. Org. Chem. 2017; 1902
4l Formenti d. Ferretti F. Ragaini F. ChemCatChem 2018; 10: 148

5 Mali M. Synth. Catal. 2017; 2: 2

6a Cadogan JI. G. Cameron-Wood M. Proc. Chem. Soc. (London) 1962; 361
6b Cadogan JI. G. Cameron-Wood M. Mackie RK. Searle RJ. G. J. Chem. Soc. 1965; 4831
6c Sundberg RJ. Tetrahedron Lett. 1965; 477
6d Cadogan JI. G. Todd MJ. J. Chem. Soc. C 1969; 2808
6e Ho TL. Hsieh SY. Helv. Chim. Acta 2006; 89: 111
6f Freeman AW. Urvoy M. Criswell ME. J. Org. Chem. 2005; 70: 5014
6g Sanz R. Escribano J. Pedrosa MR. Aguado R. Arnaiz FJ. Adv. Synth. Catal. 2007; 349: 713

7a Crotti C. Cenini S. Rindone B. Tollari S. Demartin F. J. Chem. Soc., Chem. Commun. 1986; 784
7b Annunziata R. Cenini S. Palmisano G. Tollari S. Synth. Commun. 1996; 26: 495
7c Söderberg BC. G. Wallace JM. Tamariz J. Org. Lett. 2002; 4: 1339
7d Scott TL. Söderberg BC. G. Tetrahedron Lett. 2002; 43: 1621
7e Han R. Chen S. Lee SJ. Qi F. Wu X. Kim BH. Heterocycles 2006; 68: 1675
7f Wallace JM. Söderberg BC. G. Tamariz J. Akhmedov NG. Hurley MT. Tetrahedron 2008; 64: 9675

8a Fernandes AC. Romáo CC. Tetrahedron 2006; 62: 9650
8b Fernandes AC. Romáo CC. Tetrahedron Lett. 2007; 48: 9176
8c Reis PM. Costa PJ. Romáo CC. Fernandes JA. Calhorda MJ. Royo B. Dalton Trans. 2008; 1727
8d Reis PM. Royo B. Tetrahedron Lett. 2009; 50: 949

9a Alper H. Edward JT. Can. J. Chem. 1970; 48: 1543
9b Crotti C. Cenini S. Bossoli A. Rindone B. Demartin F. J. Mol. Catal. 1991; 70: 175
9c Pizzotti M. Cenini S. Quici S. Tollari S. J. Chem. Soc., Perkin Trans. 2 1994; 913
9d For a review, see: Söderberg BC. G. Curr. Org. Chem. 2000; 4: 727
9e Smitrovich JH. Davies IW. Org. Lett. 2004; 6: 533
9f Vodnala N. Kaldhi D. Polina S. Putta VP. R. K. Gupta R. Promily SC. P. Linthoinganbi RK. Singh V. Malakar CC. Tetrahedron Lett. 2016; 57: 5695

10a Pizzotti M. Cenini S. Psaro R. Costanzi S. J. Mol. Catal. 1990; 63: 299
10b Crotti C. Cenini C. J. Chem. Soc., Faraday Trans. 1991; 87: 2811
10c Crotti C. Cenini S. Ragaini F. Porta F. Tollari S. J. Mol. Catal. 1992; 72: 283

11 Sanz R. Escribano J. Aguado R. Pedrosa MR. Arnáiz FJ. Synthesis 2004; 1629

12a Malakar CC. Merisor E. Conrad J. Beifuss U. Synlett 2010; 1766
12b Moustafa AH. Malakar CC. Aljaar N. Merisor E. Conrad J. Beifuss U. Synlett 2013; 24: 1573
12c Siddiqui IR. Srivastava A. Singh A. Shamim S. Rai P. RSC Adv. 2015; 5: 5256
12d Vodnala N. Kaldhi D. Gupta R. Polina S. Putta VP. R. K. Promily SC. P. Linthoinganbi RK. Singh V. Malakar CC. ChemistrySelect 2016; 1: 5784

13 Garcia N. Garcia-Garcia P. Fernindez-Rodriguez MA. Rubio R. Pedrosa MR. Arnaiz FJ. Sanz R. Adv. Synth. Catal. 2012; 354: 321; and references cited therein
14 Gerber NN. J. Org. Chem. 1967; 32: 4055
15 Toshima K. Takano R. Ozawa T. Matsumura S. Chem. Commun. 2002; 212

16a Anderson RK. Carter SD. Cheeseman GW. H. Tetrahedron 1979; 35: 2463
16b Zhang Z. Yin Z. Kadow JF. Meanwell NA. Wang T. Synlett 2004; 2323

17a Kidani Y. Chem. Pharm. Bull. 1959; 7: 88
17b Kumar BS. P. A. Madhav B. Reddy KH. V. Nageswar YV. D. Tetrahedron Lett. 2011; 52: 2862

Supplementary Material

Supporting Information

Efficient Syntheses of Diverse N-Heterocycles: The Molybdenum(VI)-Catalyzed Reductive Cyclization of Nitroarenes using Pinacol as a Deoxygenating­ Agent

Efficient Syntheses of Diverse N-Heterocycles: The Molybdenum(VI)-Catalyzed Reductive Cyclization of Nitroarenes using Pinacol as a Deoxygenating Agent