Addition of Alcohols onto Electron-Deficient Heteroarenium Salts: A Reversible Covalent Bonding Process under Basic Conditions

Baoli Chen; En Li; Feifei Song; Nicolas Guimond; Jiean Chen; Yong Huang

doi:10.1055/a-2005-5372

Synlett, Inhaltsverzeichnis

Synlett 2023; 34(09): 1042-1048
DOI: 10.1055/a-2005-5372

letter

Addition of Alcohols onto Electron-Deficient Heteroarenium Salts: A Reversible Covalent Bonding Process under Basic Conditions

Baoli Chen‡

^aState Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, P. R. of China

,

En Li‡

^cPingshan Translational Medicine Center, Shenzhen Bay Laboratory, Shenzhen, 518055, P. R. of China

,

Feifei Song

^aState Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, P. R. of China

,

Nicolas Guimond

^dProcess Research, Bayer AG Crop Science, 40789 Monheim, Germany

,

Jiean Chen ∗

^aState Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, P. R. of China

^cPingshan Translational Medicine Center, Shenzhen Bay Laboratory, Shenzhen, 518055, P. R. of China

,

Yong Huang∗

^bDepartment of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong SAR, P. R. of China

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

The reversible addition of benzyl alcohol onto heteroarenium salts under basic conditions was studied. Fine-tuning of the nature of the arenium and substituents allowed the discovery of a range of pyrimidinium substrates that can undergo C6-selective alcohol addition. Crossover experiments were also performed to confirm the addition-elimination equilibrium under basic conditions.

Keywords

heteroarenium salts - alcohols - reversible addition - basic conditions

Volltext

Referenzen

References and Notes

1a Clerin D, Bruice TC. J. Am. Chem. Soc. 1974; 96: 5571
1b Loechler EL, Schneider AM, Schwartz DB, Hollocher TC. J. Am. Chem. Soc. 1987; 109: 3076
1c Link JO, Straub K. J. Am. Chem. Soc. 1996; 118: 2091
1d Li K, Du W, Que NL. S, Liu H.-W. J. Am. Chem. Soc. 1996; 118: 8763
1e Wodzinska J, Snell KD, Rhomberg A, Sinskey AJ, Biemann K, Stubbe J. J. Am. Chem. Soc. 1996; 118: 6319
1f McCarthy DL, Louie DF, Copley SD. J. Am. Chem. Soc. 1997; 119: 11337
1g Murphy JE, Stec B, Ma L, Kantrowitz ER. Nat. Struct. Mol. Biol. 1997; 4: 618
1h Williams SD, David SS. Nucleic Acids Res. 1998; 26: 5123
1i Vocadlo DJ, Davies GJ, Laine R, Withers SG. Nature 2001; 412: 835
1j Xie W, Liu X, Huang RH. Nat. Struct. Mol. Biol. 2003; 10: 781
1k Kluger R, Tittmann K. Chem. Rev. 2008; 108: 1797
1l Rosenthal RG, Ebert M, Kiefer P, Peter DM, Vorholt JA, Erb TJ. Nat. Chem. Biol. 2014; 10: 50

2a Vougioukalakis GC, Grubbs RH. Chem. Rev. 2010; 110: 1746
2b Campbell MG, Ritter T. Chem. Rev. 2015; 115: 612
2c Ruiz-Castillo P, Buchwald SL. Chem. Rev. 2016; 116: 12564
2d Park Y, Kim Y, Chang S. Chem. Rev. 2017; 117: 9247
2e Dong Z, Ren Z, Thompson SJ, Xu Y, Dong G. Chem. Rev. 2017; 117: 9333
2f He J, Wasa M, Chan KS. L, Shao Q, Yu J.-Q. Chem. Rev. 2017; 117: 8754
2g Gandeepan P, Müller T, Zell D, Cera G, Warratz S, Ackermann L. Chem. Rev. 2019; 119: 2192
2h Trowbridge A, Walton SM, Gaunt MJ. Chem. Rev. 2020; 120: 2613
2i Lutz MD. R, Morandi B. Chem. Rev. 2021; 121: 300
2j Zhao B, Rogge T, Ackermann L, Shi Z. Chem. Soc. Rev. 2021; 50: 8903
2k Chan AY, Perry IB, Bissonnette NB, Buksh BF, Edwards GA, Frye LI, Garry OL, Lavagnino MN, Li BX, Liang Y, Mao E, Millet A, Oakley JV, Reed NL, Sakai HA, Seath CP, MacMillan DW. C. Chem. Rev. 2022; 122: 1485
2l Sinha SK, Guin S, Maiti S, Biswas JP, Porey S, Maiti D. Chem. Rev. 2022; 122: 5682

3a Enders D, Balensiefer T. Acc. Chem. Res. 2004; 37: 534
3b Enders D, Niemeier O, Henseler A. Chem. Rev. 2007; 107: 5606
3c MacMillan DW. C. Nature 2008; 455: 304
3d Izquierdo J, Hutson GE, Cohen DT, Scheidt KA. Angew. Chem. Int. Ed. 2012; 51: 11686
3e Mahatthananchai J, Bode JW. Acc. Chem. Res. 2014; 47: 696
3f Hopkinson MN, Richter C, Schedler M, Glorius F. Nature 2014; 510: 485
3g Flanigan DM, Romanov-Michailidis F, White NA, Rovis T. Chem. Rev. 2015; 115: 9307
3h Chen X, Gao Z, Ye S. Acc. Chem. Res. 2020; 53: 690

4a Jang H, Hong J, MacMillan DW. C. J. Am. Chem. Soc. 2007; 129: 7004
4b List B, Lerner RA, Barbas CF. III. J. Am. Chem. Soc. 2000; 122: 2395
4c Qin Y, Zhu L, Luo S. Chem. Rev. 2017; 117: 9433
4d Zhan G, Du W, Chen Y.-C. Chem. Soc. Rev. 2017; 46: 1675
4e Reyes-Rodríguez GJ, Rezayee NM, Vidal-Albalat A, Jørgensen KA. Chem. Rev. 2019; 119: 4221

5a Ahrendt KA, Borths CJ, MacMillan DW. C. J. Am. Chem. Soc. 2000; 122: 4243
5b Mayer S, List B. Angew. Chem. Int. Ed. 2006; 45: 4193
5c Brak K, Jacobsen EN. Angew. Chem. Int. Ed. 2013; 52: 534
5d Mahlau M, List B. Angew. Chem. Int. Ed. 2013; 52: 518
5e Phipps RJ, Hamilton GL, Toste FD. Nat. Chem. 2012; 4: 603

6a Dhawa U, Tian C, Wdowik T, Oliveira JC. A, Hao J, Ackermann L. Angew. Chem. Int. Ed. 2020; 59: 13451
6b Xia Y, Dong G. Nat. Rev. Chem. 2020; 4: 600
6c Chen H, Liao G, Xu C, Yao Q, Zhang S, Shi B. CCS Chem. 2021; 3: 455
6d Liu Z, Oxtoby LJ, Liu M, Li Z, Tran VT, Gao Y, Engle KM. J. Am. Chem. Soc. 2021; 143: 8962
6e Liu M, Sun J, Erbay TG, Ni H, Martín-Montero R, Liu P, Engle KM. Angew. Chem. Int. Ed. 2022; 61: e202203624
6f Li Y, Ouyang Y, Chekshin N, Yu J.-Q. J. Am. Chem. Soc. 2022; 144: 4727

7a Procuranti B, Connon SJ. Org. Lett. 2008; 10: 4935
7b Berkessel A, Das S, Pekel D, Neudörfl J. Angew. Chem. Int. Ed. 2014; 53: 11660
7c Das S, Pekel D, Neudörfl J, Berkessel A. Angew. Chem. Int. Ed. 2015; 54: 12479

8a Leleu S, Papamicaël C, Marsais F, Dupas G, Levacher V. Tetrahedron: Asymmetry 2004; 15: 3919
8b Ménová P, Kafka F, Dvořáková H, Gunnoo S, Šanda M, Cibulka R. Adv. Synth. Catal. 2011; 353: 865
8c Hartman T, Šturala J, Cibulka R. Adv. Synth. Catal. 2015; 357: 3573
8d Šturala J, Boháčová S, Chudoba J, Metelková R, Cibulka R. J. Org. Chem. 2015; 80: 2676

9a Speelman JC, Kellogg RM. J. Org. Chem. 1990; 55: 647
9b Dong Z, MacMillan DW. C. Nature 2021; 598: 451

10 Sakai T, Kumoi T, Ishikawa T, Nitta T, Iida H. Org. Biomol. Chem. 2018; 16: 3999
11 Gómez-Bujedo S, Alcarazo M, Pichon C, Álvarez E, Fernández R, Lassaletta JM. Chem. Commun. 2007; 1180
12 Synthesis of Compound 3a–z; General Procedure: Pyridinium salt (0.05 mmol), alcohol (1.0 equiv), base (2.0 equiv) and 4Å molecule sieves (100 mg) in CD₃CN (0.5 mL) were stirred for 1 hour under argon in room temperature. Yield was determined by ¹H NMR analysis of the crude mixture with 1,4-dinitrobenzene (0.5 equiv) as internal standard. 6-(Benzyloxy)-1-methyl-1,6-dihydropyrimidine (3a) Yield: 23%. ¹H NMR (400 MHz, CD₃CN): δ = 7.33–7.29 (m, 5 H), 6.79 (d, J = 7.0 Hz, 1 H), 5.61 (d, J = 4.3 Hz, 1 H), 5.19 (ddd, J = 7.0, 4.4, 1.2 Hz, 1 H), 4.33 (d, J = 11.4 Hz, 1 H), 4.12 (d, J = 11.4 Hz, 1 H), 3.04 (s, 3 H).

Zusatzmaterial

Supporting Information