MeONH2·HCl-Mediated α-Methylenation/Conjugate Addition of α-Sulfonyl o-Hydroxyacetophenones with Methyl Sulfoxides: Route to 3-Sulfonylchroman-4-ones

Meng-Yang Chang; Kuan-Ting Chen

doi:10.1055/s-0040-1707245

Synthesis, Table of Contents

Synthesis 2021; 53(01): 135-145
DOI: 10.1055/s-0040-1707245

paper

MeONH₂·HCl-Mediated α-Methylenation/Conjugate Addition of α-Sulfonyl o-Hydroxyacetophenones with Methyl Sulfoxides: Route to 3-Sulfonylchroman-4-ones

Meng-Yang Chang ∗

^aDepartment of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan Email: mychang@kmu.edu.tw

^bDepartment of Medical Research, Kaohsiung Medical University Hospital, Kaohsiung 807, Taiwan

,

Kuan-Ting Chen

^aDepartment of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan Email: mychang@kmu.edu.tw

› Author Affiliations

Abstract

All articles of this category

Abstract

A novel and efficient route for the synthesis of 3-sulfonylchroman-4-ones from α-sulfonyl o-hydroxyacetophenones with methyl sulfoxides via a MeONH₂·HCl-mediated sequential methylenation/ conjugate addition is described. Plausible reaction mechanisms are proposed and discussed. Various reaction conditions for this novel, one-pot, environmentally friendly conversion were investigated.

Key words

chroman-4-ones - o-hydroxyacetophenones - methylenation - methyl sulfoxides - sulfonyl compounds

Full Text

References

References
1 Xiang J.-C, Gao Q.-H, Wu A.-X. The Applications of DMSO. In Solvents as Reagents in Organic Synthesis: Reactions and Applications. Wu X.-F. Wiley-VCH; Weinheim: 2017. Chap. 7

Recent examples for CH₂Cl₂, see:

2a Liu Y, Song R.-J, Luo S, Li J.-H. Org. Lett. 2018; 20: 212
2b Zhao Y, Chen X, Chen T, Zhou Y, Yin S.-F, Han L.-B. J. Org. Chem. 2015; 80: 62
2c Chen X, Chen T, Zhou Y, Au C.-T, Han L.-B, Yin S.-F. Org. Biomol. Chem. 2014; 12: 247
2d Yu D, Zhang Y. Adv. Synth. Catal. 2011; 353: 163

Recent examples for DMF and DMA, see:

3a Pu F, Li Y, Song Y.-H, Xiao J, Liu Z.-W, Wang C, Liu Z.-T, Chen J.-G, Lu J. Adv. Synth. Catal. 2016; 358: 539
3b Modi A, Ali W, Patel BK. Adv. Synth. Catal. 2016; 358: 2100
3c Kaswan P, Nandwana NK, DeBoef B, Kumar A. Adv. Synth. Catal. 2016; 358: 2108

Recent examples for DMSO, see:

4a Ebule R, Mudshinge S, Nantz MH, Mashuta MS, Hammond GB, Xu B. J. Org. Chem. 2019; 84: 3249
4b Wen Z.-K, Liu X.-H, Liu Y.-F, Chao J.-B. Org. Lett. 2017; 19: 5798
4c Xue L, Cheng G, Zhu R, Cui X. RSC Adv. 2017; 7: 44009
4d Sun K, Zhu ZH, Sun JJ, Liu LL, Wang X. J. Org. Chem. 2016; 81: 1476
4e Li PF, Weng YX, Xu XX, Cui XL. J. Org. Chem. 2016; 81: 3994
4f Patel OP. S, Anand D, Maurya RK, Yadav PP. J. Org. Chem. 2016; 81: 7626
4g Liu P, Shen ZY, Yuan Y, Sun PP. Org. Biomol. Chem. 2016; 14: 6523
4h Sun K, Wang X, Jiang Y, Lv Y, Zhang L, Xiao B, Li D, Zhu Z, Liu L. Chem. Asian J. 2015; 10: 536
4i Mahajan PS, Tanpure SD, More NA, Gajbhiye JM, Mhaske SB. RSC Adv. 2015; 5: 101641
4j Sun K, Lv Y, Zhu Z, Zhang L, Wu H, Liu L, Jiang Y, Xiao B, Wang X. RSC Adv. 2015; 5: 3094
4k Wang J, Rochon FD, Yang Y, Hua L, Kayser MM. Tetrahedron: Asymmetry 2007; 18: 1115

Recent examples for toluene, see:

5a Luo WK, Shi X, Zhou W, Yang L. Org. Lett. 2016; 18: 2036
5b Li K, Wu Q, Lan J, You J. Nat. Commun. 2015; 6: 8404

Recent examples for MeCN, see:

6a Wang C, Li Y, Gong M, Wu Q, Zhang J, Kim JK, Huang M, Wu Y. Org. Lett. 2016; 18: 4151
6b Bunescu A, Wang Q, Zhu J. Org. Lett. 2015; 17: 1890
6c Li Y, Liu B, Li H.-B, Wang Q, Li J.-H. Chem. Commun. 2015; 51: 1024

Recent examples for MeNO₂, see:

7a Padilla-Salinas R, Walvoord RR, Tcyrulnikov S, Kozlowski MC. Org. Lett. 2013; 15: 3966
7b Akagawa K, Kudo K. Angew. Chem. Int. Ed. 2012; 51: 12786

Reviews on DMSO-mediated reactions, see:

8a Jones-Mensah E, Karki M, Magolan J. Synthesis 2016; 48: 1421
8b Wu X.-F, Natte K. Adv. Synth. Catal. 2016; 358: 336
8c Tashrifi Z, Khanaposhtani MM, Larijani B, Mahdavia M. Adv. Synth. Catal. 2020; 362: 65

Examples of DMSO-mediated α-methylenation, see:

9a Zhu H, Meng X, Zhang Y, Chen G, Cao Z, Sun X, You J. J. Org. Chem. 2017; 82: 12059
9b Liu Y.-F, Ji P.-Y, Xu J.-W, Hu Y.-Q, Liu Q, Luo W.-P, Cuo C.-C. J. Org. Chem. 2017; 82: 7159
9c Pothikumar R, Sujatha C, Namitharan K. ACS Catal. 2017; 7: 7783

Examples of 3-substituted chroman-4-one syntheses, see:

10a Tang L, Yang Z, Chang X, Jiao J, Ma X, Rao W, Zhou Q, Zheng L. Org. Lett. 2018; 20: 6520
10b Hu H, Chen X, Sun K, Wang J, Liu Y, Liu H, Fan L, Yu B, Sun Y, Qu L, Zhao Y. Org. Lett. 2018; 20: 6157
10c Lu D, Wan Y, Kong L, Zhu G. Org. Lett. 2017; 19: 2929
10d Rafiński Z, Kozakiewicz A. J. Org. Chem. 2015; 80: 7468
10e Ankner T, Fridén-Saxin M, Pemberton N, Seifert T, Grøtli M, Luthman K, Hilmersson G. Org. Lett. 2010; 12: 2210
10f de Alaniz JR, Kerr MS, Moore JL, Rovis T. J. Org. Chem. 2008; 73: 2033

Examples of biologically active 3-substituted chroman-4-ones, see:

11a Basavarajappa HD, Lee B, Lee H, Sulaiman RS, An H, Magaña C, Shadmand M, Vayl A, Rajashekhar G, Kim E.-Y, Suh Y.-G, Lee K, Seo S.-Y, Corson TW. J. Med. Chem. 2015; 58: 5015
11b Seifert T, Malo M, Kokkola T, Engen K, Fridén-Saxin M, Wallén EA. A, Lahtela-Kakkonen M, Jarho EM, Luthman K. J. Med. Chem. 2014; 57: 9870
11c Amato E, Bankemper T, Kidney R, Do T, Ma L. Bioorg. Med. Chem. 2014; 22: 126
11d Guo H, Zhao H, Kanno Y, Li W, Bai H. Bioorg. Med. Chem. Lett. 2013; 23: 3137
11e Conti C, Monaco LP, Desideri N. Bioorg. Med. Chem. 2011; 19: 7357

Examples of sulfonylchroman-4-one syntheses, see:

12a Chang M.-Y, Wu Y.-S, Chen H.-Y. Org. Lett. 2018; 20: 1824
12b Chang M.-Y, Chen H.-Y, Tsai Y.-L. J. Org. Chem. 2019; 84: 326
12c Yang D.-T, Meng Q.-Y, Zhong J.-J, Xiang M, Liu Q, Wu L.-Z. Eur. J. Org. Chem. 2013; 7528
12d Wan J.-P, Zhong S, Guo Y, Wei L. Eur. J. Org. Chem. 2017; 4401

Reviews on Umpolung reactions, see:

13a Miyata O, Miyoshi T, Ueda M. ARKIVOC 2013; (ii): 60
13b Izquierdo J, Hutson GE, Cohen DT, Scheidt KA. A. Angew. Chem. Int. Ed. 2012; 51: 11686

Selected examples of Umpolung conjugation of C–S bonds. For α-sulfenyl ketones, see:

14a Hatcher JM, Kohler MC, Coltart DM. Org. Lett. 2011; 13: 3810
14b Gabillet S, Lecerclé D, Loreau O, Carboni M, Dézard S, Gomis JM, Taran F. Org. Lett. 2007; 9: 3925

For β-sulfenyl ketones, see:

14c Fan J, Zhao Y, Zhang J, Xie M, Zhang Y. J. Org. Chem. 2020; 85: 691
14d Mizota I, Ueda C, Tesong Y, Tsujimoto Y, Shimizu M. Org. Lett. 2018; 20: 2291

For β,β-disulfenyl ketones, see:

14e Lai J, Tian L, Huo X, Zhang Y, Xie X, Tang S. J. Org. Chem. 2015; 80: 5894

15 Chang M.-Y, Chen H.-Y, Tsai Y.-L. Org. Lett. 2019; 21: 1832
16 CCDC 1938200 (4a), 1938201 (4f), 1945748 (4x), 1938202 (5a) and 1938203 (5b) 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.

17a Chu L, Yue X, Qing F.-L. Org. Lett. 2010; 12: 1644
17b Luo F, Pan C, Li L, Chen F, Cheng J. Chem. Commun. 2011; 47: 5304
17c Wang M, Tang B.-C, Ma J.-T, Wang Z.-X, Xiang J.-C, Wu Y.-D, Wang J.-G, Wu A.-X. Org. Biomol. Chem. 2019; 17: 1535

18 Traynelis VJ, Hergenrother WL. J. Org. Chem. 1964; 29: 221
19 Sharma P, Rohilla S, Jain N. J. Org. Chem. 2015; 80: 4116
20 Review on desulfonylation reactions, see: Nájera C, Yus M. Tetrahedron 1999; 55: 10547

Reviews on sulfur chemistry, see:

21a Wang M, Li Y, Jiang X. Aldrichimica Acta 2020; 53: 19
21b Qiaz Z, Jiang X. Org. Biomol. Chem. 2017; 15: 1942
21c Liu H, Jiang X. Chem. Asian J. 2013; 8: 2546

22 Review on the Knoevenagel reaction, see: Majumdar KC, Taher A, Nandi RK. Tetrahedron 2012; 68: 5693

Selected examples of Knoevenagel reactions, see:

23a Yang D.-S, Ke S, Du X, Gao P, Zhu H.-T, Fan MJ. Tetrahedron 2017; 73: 5522
23b Kumpf J, Schwaebel ST, Bunz UH. F. J. Org. Chem. 2015; 80: 5159
23c Lakshmi V, Ravikanth M. J. Org. Chem. 2013; 78: 4993
23d Srinivas V, Koketsu M. J. Org. Chem. 2013; 78: 11612

Supplementary Material