Tandem Deoxygenative Geminal Fluorosulfonimidation of 1,2-Diketones via Formal N–F Insertion Enabled by Dealkylation-Resistant Phosphoramidite

Sujin Bak; Yeri Son; Sunjoo Hwang; Ha Eun Kim; Jun-Ho Choi; Won-jin Chung

doi:10.1055/a-2005-4296

Synthesis, Table of Contents

Synthesis 2023; 55(10): 1533-1542
DOI: 10.1055/a-2005-4296

paper

Tandem Deoxygenative Geminal Fluorosulfonimidation of 1,2-Diketones via Formal N–F Insertion Enabled by Dealkylation-Resistant Phosphoramidite

Sujin Bak‡

,

Yeri Son‡

,

Sunjoo Hwang

,

Ha Eun Kim

,

Jun-Ho Choi∗

,

Won-jin Chung∗

Abstract

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Abstract

Our group has recently developed an α-fluoroamine synthesis using dioxaphospholenes derived from various 1,2-diketones and the dealkylation-resistant phosphoramidite as carbene surrogates, enabling the formal insertion into the N–F bond of (PhSO₂)₂NF. This full account presents the scope and limitations in terms of the reactivity and the site selectivity; these were rationalized through computational analysis. In addition, the efforts to broaden the synthetic utility of the current process by incorporating other nitrogen nucleophiles and halogen electrophiles are described.

Key words

fluoroamine - sulfonimide - dioxaphospholene - carbene surrogate - phosphoramidite - N–F insertion - geminal difunctionalization - 1,2-diketone

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References

References
1 Morgenthaler M, Schweizer E, Hoffmann-Röder A, Benini F, Martin RE, Jaeschke G, Wagner B, Fischer H, Bendels S, Zimmeril D, Schneider J, Diederich F, Kansy M, Müller K. ChemMedChem 2007; 2: 1100

2a Donetti A, Cereda E, Ezhaya A, Micheletti R. J. Med. Chem. 1989; 32: 957
2b van Niel MB, Collins I, Beer MS, Broughton HB, Cheng SK. F, Goodacre SC, Heald A, Locker KL, Mac-Leod AM, Morrison D, Moyes CR, O’Connor D, Pike A, Rowley M, Russell MG. N, Sohal B, Stanton JA, Thomas S, Verrier H, Watt AP, Castro JL. J. Med. Chem. 1999; 42: 2087
2c Jeschke P. ChemBioChem 2004; 5: 570
2d Böhm H.-J, Banner D, Bendels S, Kansy M, Kuhn B, Müller K, ObstSander U, Stahl M. ChemBioChem 2004; 5: 637
2e Isanbor C, O’Hagan D. J. Fluorine Chem. 2006; 127: 303
2f Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
2g Kirk KL. Org. Process Res. Dev. 2008; 12: 305
2h Hagmann WK. J. Med. Chem. 2008; 51: 4359
2i O’Hagan D. Chem. Soc. Rev. 2008; 37: 308
2j Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
2k Hunter L. Beilstein J. Org. Chem. 2010; 6: 38
2l Gills EP, Eastman KJ, Hill MD, Donnelly DJ, Meanwell NA. J. Med. Chem. 2015; 58: 8315
2m Zhou Y, Wang J, Gu Z, Wang S, Zhu W, Aceña JL, Soloshonok VA, Izawa K, Liu H. Chem. Rev. 2016; 116: 422
2n Meanwell NA. J. Med. Chem. 2018; 61: 5822

3a Stavber S, Pecan TS, Papež M, Zupan M. Chem. Commun. 1996; 2247
3b Yadav JS, Reddy BV. S, Chary DN, Chandrakanth D. Tetrahedron Lett. 2009; 50: 1136
3c Wu T, Yin G, Liu G. J. Am. Chem. Soc. 2009; 131: 16354
3d Qiu S, Xu T, Zhou J, Guo Y, Liu G. J. Am. Chem. Soc. 2010; 132: 2856
3e Duthion B, Pardo DG, Cossy J. Org. Lett. 2010; 12: 4620
3f Kalow JA, Schmitt DE, Doyle AG. J. Org. Chem. 2012; 77: 4177
3g Wang Q, Zhong W, Wei X, Ning M, Meng X, Li Z. Org. Biomol. Chem. 2012; 10: 8566
3h Kong W, Feige P, de Haro T, Nevado C. Angew. Chem. Int. Ed. 2013; 52: 2469
3i Suzuki S, Kamo T, Fukushi K, Hiramatsu T, Tokunaga E, Dohi T, Kita Y, Shibata N. Chem. Sci. 2014; 5: 2754
3j Zhang H, Song Y, Zhao J, Zhang J, Zhang Q. Angew. Chem. Int. Ed. 2014; 53: 11079
3k Chen P, Liu G. Eur. J. Org. Chem. 2015; 4295
3l Saavedra-Olavarría J, Arteaga GC, López JJ, Pérez EG. Chem. Commun. 2015; 51: 3379
3m Lu D.-F, Zhu C.-L, Sears JD, Xu H. J. Am. Chem. Soc. 2016; 138: 11360
3n Serguchev YA, Ponomarenko MV, Ignatév NV. J. Fluorine Chem. 2016; 185: 1
3o Hou C, Chen P, Liu G. Angew. Chem. Int. Ed. 2020; 59: 2735
3p Feng G, Ku CK, Zhao J, Wang Q. J. Am. Chem. Soc. 2022; 144: 20463

4a Chen G, Song J, Yu Y, Luo X, Li C, Huang X. Chem. Sci. 2016; 7: 1786
4b Zhou Y, Zhang Y, Wang J. Org. Biomol. Chem. 2016; 14: 10444
4c Huang J, Li L, Chen H, Xiao T, He Y, Zhou L. Org. Chem. Front. 2017; 4: 529

5a Ramirez F, Mitra RB, Desai NB. J. Am. Chem. Soc. 1960; 82: 2651
5b Ramirez F, Desai NB. J. Am. Chem. Soc. 1960; 82: 2652
5c Ramirez F. Pure Appl. Chem. 1964; 9: 337
5d Ramirez F. Synthesis 1974; 90
5e Ramirez F, Kugler HJ, Smith CP. Tetrahedron 1968; 24: 3153
5f Ramirez F. Acc. Chem. Res. 1968; 1: 168
5g Miller EJ, Zhao W, Herr JD, Radosevich AT. Angew. Chem. Int. Ed. 2012; 51: 10605
5h Zhao W, Fink DM, Labutta CA, Radosevich AT. Org. Lett. 2013; 15: 3090
5i Wang SR, Radosevich AT. Org. Lett. 2015; 17: 3810
5j For a recent review, see: Liu Y, Sun F, He Z. Tetrahedron Lett. 2018; 59: 4136

For recent applications of the Kukhtin–Ramirez reaction, see:

6a Tan P, Wang SR. Org. Lett. 2019; 21: 6029
6b Zhang J, Hao J, Huang Z, Han J, He Z. Chem. Commun. 2020; 56: 10251
6c Liu R, Liu J, Cao J, Li R, Zhou R, Qiao Y, Gao W.-C. Org. Lett. 2020; 22: 6922
6d Deng Y.-H, Chu W.-D, Shang Y.-H, Yu K.-Y, Jia Z.-L, Fan C.-A. Org. Lett. 2020; 22: 8376
6e Jin S, Dang HT, Haug GC, Nguyen VD, Arman HD, Larionov OV. Chem. Sci. 2020; 11: 9101
6f Tan P, Wang H, Wang SR. Org. Lett. 2021; 23: 2590
6g Zhang J, Qiu Y, Zhang B, Huang Z, He Z. Org. Lett. 2021; 23: 1880
6h Zhang Z, Jing L, Li E.-Q, Duan Z. Org. Chem. Front. 2022; 9: 3215

7a Choi G, Kim HE, Hwang S, Jang H, Chung W.-j. Org. Lett. 2020; 22: 4190
7b Son Y, Hwang S, Bak S, Kim HE, Choi J.-H, Chung W.-j. Org. Biomol. Chem. 2022; 20: 3263

8a Chinchilla R, Najera C. Chem. Rev. 2007; 107: 874
8b Chinchilla R, Najera C. Chem. Soc. Rev. 2011; 40: 5084
8c Jung D.-Y, Park SY, Kim S.-H. Bull. Korean Chem. Soc. 2022; 43: 110

9 Park K, Bae G, Cheo J, Song KH, Lee S. J. Org. Chem. 2010; 75: 6244

10a Stuart DR, Bertrand-Laperle M, Burgess KM. N, Fagnou K. J. Am. Chem. Soc. 2008; 130: 16474
10b Yan Q, Shen X, Zi G, Hou G. Chem. Eur. J. 2020; 26: 5961

11a Xu Y, Wan X. Tetrahedron Lett. 2013; 54: 642
11b Ren W, Liu J, Long C, Wan X. Adv. Synth. Catal. 2010; 352: 1424

12 Sibi MP, Marvin M, Sharma R. J. Org. Chem. 1995; 60: 5016

13a Harrington LE, Britten JF, Hughes DW, Bain AD, Thépot J.-Y, McGlinchey MJ. J. Organomet. Chem. 2002; 656: 243
13b Reddy SR, Stella S, Chadha A. Synth. Commun. 2012; 42: 3493

14a Hammett LP. J. Am. Chem. Soc. 1937; 59: 96
14b Hammett LP. Chem. Rev. 1935; 17: 125
14c Hansch C, Leo A, Taft RW. Chem. Rev. 1991; 91: 165

15 CCDC 2110574 and CCDC 2110575 contain the supplementary crystallographic data for this study. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
16 In our related study on geminal chlorofluorination,^7a chloride anion was nucleophilic enough to produce both constitutional isomers from 4n.

17a The alkene geometry was assigned through comparison with the reported ¹H–¹⁹F coupling constant of related compounds; see: Zhang H, Lin J.-H, Xiao J.-C, Gu Y.-C. Org. Biomol. Chem. 2014; 12: 581

See also:

17b Brady SF, Ilton MA, Johnson WS. J. Am. Chem. Soc. 1968; 90: 2882
17c Sarel S, Yovell J, Sarel-Imber M. Angew. Chem. Int. Ed. 1968; 7: 577

18a Shohji N, Kawaji T, Okamoto S. Org. Lett. 2011; 13: 2626
18b Zhou A, Shao Y, Chen F, Qian P.-C, Cheng J. Tetrahedron Lett. 2022; 89: 153597

19 The imine geometry was assigned on the basis of computational calculation. The Z-isomer is more stable by 2.7 kcal/mol at the M06-2X-D3/6-31+G(d,p)/PCM(CH₂Cl₂) level.
20 Cho E, Kim M, Jayaraman A, Kim J, Lee S. Eur. J. Org. Chem. 2018; 781
21 Geminal aminochlorination has previously been shown to be challenging with diazo compounds.^4a
22 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA. Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ. Gaussian 16, Revision C.01. Gaussian, Inc; Wallingford CT: 2019
23 The initial input geometry was obtained by Molecular Orbital Package 2016: Stewart JJ. P. MOPAC2016. Stewart Computational Chemistry; Colorado Springs: 2016. http//openmopac.net/

24a Zhao Y, Truhlar DG. Theor. Chem. Acc. 2008; 120: 215
24b Zhao Y, Truhlar DG. Acc. Chem. Res. 2008; 41: 157

25a Grimme S, Antony J, Ehrlich S, Krieg H. J. Chem. Phys. 2010; 132: 154104
25b Peverati R, Baldridge KK. J. Chem. Theory Comput. 2008; 4: 2030

26a Miertuš S, Scrocco E, Tomasi J. Chem. Phys. 1981; 55: 117
26b Pascual-Ahuir JL, Silla E, Tuñón I. J. Comput. Chem. 1994; 15: 1127
26c Barone V, Cossi M. J. Phys. Chem. A 1998; 102: 1995

27a de Meijere A. Angew. Chem. Int. Ed. 1979; 18: 809
27b Olah GA, Reddy VP, Prakash GK. S. Chem. Rev. 1992; 92: 69

28 Nielsen DK, Doyle AG. Angew. Chem. Int. Ed. 2011; 50: 6056
29 Liang J, Han J, Wu J, Wu P, Hu J, Hu F, Wu F. Org. Lett. 2019; 21: 6844

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