Direct 2-Pyridyl-Alkylation of Benzyne with N-Alkylpyridinium Salts

Ning-Xin Guo; Ji-Bao Xia; Yijin Su

doi:10.1055/a-2050-6508

Synthesis, Inhaltsverzeichnis

Synthesis 2023; 55(14): 2159-2165
DOI: 10.1055/a-2050-6508

paper

Direct 2-Pyridyl-Alkylation of Benzyne with N-Alkylpyridinium Salts

Ning-Xin Guo

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China

,

Ji-Bao Xia ∗

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

,

Yijin Su∗

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

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Abstract

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Abstract

A 2-pyridyl-alkylation of benzyne using N-alkylpyridinium salts has been developed under either photochemical or thermal conditions. This metal-free dicarbofunctionalization of benzyne undergoes a de Mayo-type process including cascade dearomative [3+2] cycloaddition and rearomative ring-opening reaction. An electron-deficient N-cyclic alkyl group was necessary. A formal ortho-C–H arylation of pyridine has been achieved.

Key words

benzyne - N-alkylpyridinium salts - dicarbofunctionalization - visible light - C–H arylation - de Mayo-type reaction

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Referenzen

References

1a Stoermer R, Kahlert B. Ber. Dtsch. Chem. Ges. 1902; 35: 1633
1b Bachmann WE, Clarke HT. J. Am. Chem. Soc. 1927; 49: 2089
1c Wittig G. Naturwissenschaften 1942; 30: 696
1d Roberts JD, Simmons HE, Carlsmith LA, Vaughan CW. J. Am. Chem. Soc. 1953; 75: 3290

2a Shi JR, Li LG, Li Y. Chem. Rev. 2021; 121: 3892
2b García-López J.-A, Greaney MF. Chem. Soc. Rev. 2016; 45: 6766
2c Tadross PM, Stoltz BM. A. Chem. Rev. 2012; 112: 3550

3a Jayanth TT, Jeganmohan M, Cheng C.-H. Org. Lett. 2005; 7: 2921
3b Jayanth TT, Cheng CH. Angew. Chem. Int. Ed. 2007; 46: 5921

4a Seo E.-K, Huang L, Wall ME, Wani MC, Navarro H, Mukherjee R, Farnsworth NR, Kinghorn AD. J. Nat. Prod. 1999; 62: 1484
4b Takoka S, Nakade K, Fukuyama Y. Tetrahedron Lett. 2002; 43: 6919

5 He J, Jia Z, Tan H, Luo X, Qiu D, Shi J, Xu H, Li Y. Angew. Chem. Int. Ed. 2019; 58: 18513

6a Piers E. Pure Appl. Chem. 1988; 60: 107
6b Huang H.-M, Bellotti P, Ma JJ, Dalton T, Glorius F. Nat. Rev. Chem. 2021; 5: 301

7a Hu R.-B, Sun S, Su Y. Angew. Chem. Int. Ed. 2017; 56: 10877
7b Chen SJ, Chen GS, Deng T, Li J.-H, He Z.-Q, Liu L.-S, Ren H, Liu Y.-L. Org. Lett. 2022; 24: 702

8a Xie C, Zhang Y, Xu P. Synlett 2008; 3115
8b Huang X, Zhang T. Tetrahedron Lett. 2009; 50: 208

9 Tambar UK, Stoltz BM. J. Am. Chem. Soc. 2005; 127: 5340

10a Yoshida H, Watanabe M, Morishita T, Ohshita J, Kunai A. Chem. Commun. 2007; 1505
10b Samineni R, Bandi CR. C, Srihari P, Mehta G. Org. Lett. 2016; 18: 6184
10c Kranthikumar R, Chegondi R, Chandrasekhar S. J. Org. Chem. 2016; 81: 2451

C–H arylation of pyridine using arynes:

11a Rao UN, Sathunuru R, Maguire JA, Biehl E. J. Heterocycl. Chem. 2004; 41: 13
11b Raminelli C, Liu Z, Larock RC. J. Org. Chem. 2006; 71: 4689
11c Shaibu BS, Kawade RK, Liu R.-S. Org. Biomol. Chem. 2012; 10: 6834
11d Lv C, Wan C, Liu S, Lan Y, Li Y. Org. Lett. 2018; 20: 1919

The de Mayo cascade includes [2+2] photocycloaddition/ring strain-driven ring opening:

12a de Mayo P, Takeshita H, Sattar AB. M. A. Proc. Chem. Soc. 1962; 119
12b de Mayo P, Takeshita H. Can. J. Chem. 1963; 41: 440
12c Martinez-Haya R, Marzo L, König B. Chem. Commun. 2018; 54: 11602
12d Salaverri N, Mas-Ballesté R, Marzo L, Alemán J. Commun. Chem. 2020; 3: 132

Dearomatization-rearomatization strategy:

13a Chen Z, Zeng H, Girard SA, Wang F, Chen N, Li C.-J. Angew. Chem. Int. Ed. 2015; 54: 14487
13b Qiu Z, Zeng H, Li C.-J. Acc. Chem. Res. 2020; 53: 2395

Generation of pyridinium ylides:

14a Dega-Szafran Z, Schroeder G, Szafran M. J. Phys. Org. Chem. 1999; 12: 39
14b Dega-Szafran Z, Schroeder G, Szafran M, Szwajca A, Łęska B, Lewandowska M. J. Mol. Struct. 2000; 555: 31
14c Szafran M, Szwajca A, Łeska B, Schroeder G, Dega-Szafran Z. J. Mol. Struct. 2002; 643: 55
14d Szwajca A, Łeska B, Schroeder G, Szafran M. J. Mol. Struct. 2004; 708: 87

15 Generation of arynes from o-trimethylsilylphenyl triflate: Himeshima Y, Sonoda T, Kobayashi H. Chem. Lett. 1983; 12: 1211
16 Deprotonation of the dearomatized carbon in the intermediate I might lead to fragmentation, which could provide the desired product.
17 Construction of spiro tetrahydroindolizine by [3+2] cycloadditon of N-alkylpyridinium salts and alkenes: He X.-L, Wang C, Wen Y.-W, Zhao Y.-B, Yang H, Qian S, Yang L, Wang Z. Org. Chem. Front. 2021; 8: 5847
18 Shao PC, Yu TY, Lu H, Xu P.-F, Wei H. CCS Chem. 2021; 3: 1862

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