Dealkenylative Functionalizations: Conversion of Alkene C(sp3)–C(sp2) Bonds into C(sp3)–X Bonds via Redox-Based Radical Processes

Brady W. Dehnert; Jeremy H. Dworkin; Ohyun Kwon

doi:10.1055/a-2044-4571

Synthesis, Inhaltsverzeichnis

Synthesis 2024; 56(01): 71-86
DOI: 10.1055/a-2044-4571

special topic

Advances in Skeletal Editing and Rearrangement Reactions

Dealkenylative Functionalizations: Conversion of Alkene C(sp³)–C(sp²) Bonds into C(sp³)–X Bonds via Redox-Based Radical Processes

Autoren

Brady W. Dehnert
Jeremy H. Dworkin
Ohyun Kwon∗

Abstract

Alle Artikel dieser Rubrik

Abstract

This review highlights the history and recent advances in dealkenylative functionalization. Through this deconstructive strategy, radical functionalizations occur under mild, robust conditions. The reactions described proceed with high efficiency, good stereoselectivity, tolerate many functional groups, and are completed within a matter of minutes. By cleaving the C(sp³)–C(sp²) bond of terpenes and terpenoid-derived precursors, rapid diversification of natural products is possible.

1 Introduction

2 Mechanism

3 History

4 Motivation to Pursue Dealkenylation

5 Dealkenylation in the Present

6 Conclusion

Key words

hydroperoxide - radical - iron(II) - dealkenylation - β-scission - terpenes

Volltext

Referenzen

References
1 Ertl P, Schuhmann T. J. Nat. Prod. 2019; 82: 1258
2 Murai S, Sonoda N, Tsutsumi S. Bull. Chem. Soc. Jpn. 1964; 37: 1187
3 Schreiber SL. J. Am. Chem. Soc. 1980; 102: 6163
4 Cardinale G, Grimmelikhuysen JC, Laan JA. M, van Lier FP, van der Steen D, Ward JP. Tetrahedron 1989; 18: 5971
5 Rosales A, Muñoz-Bascón J, López-Sánchez C, Álvarez-Corral M, Muñoz-Dorado M, Rodríguez-García I, Oltra JE. J. Org. Chem. 2012; 77: 4171
6 Bao J, Tian H, Yang P, Deng J, Gui J. Eur J. Org. Chem. 2020; 339

7a Chen S.-C, Zhu Q, Cao Y, Li C, Guo Y, Kong L, Che J, Guo Z, Chen H, Zhang N, Fang X, Lu J.-T, Luo T. J. Am. Chem. Soc. 2021; 143: 14046
7b Chen S.-C, Zhu Q, Chen H, Chen Z, Luo T. Chem. Eur. J. 2023; e202203425

8 Smaligo AJ, Vardhineedi S, Kwon O. ACS Catal. 2018; 8: 5188
9 Smaligo AJ, Swain M, Quintana JC, Tan MF, Kim DA, Kwon O. Science 2019; 364: 681
10 Smaligo AJ, Kwon O. Org. Lett. 2019; 21: 8592
11 Smaligo AJ, Wu J, Burton RN, Hacker AS, Shaikh AC, Quintana JC, Wang R, Xie C, Kwon O. Angew. Chem. Int. Ed. 2020; 59: 1211
12 Swain M, Sadykhov G, Wang R, Kwon O. Angew. Chem. Int. Ed. 2020; 59: 17565
13 Swain M, Bunnell T, Kim J, Kwon O. J. Am. Chem. Soc. 2022; 144: 14828

14a C–C Bond Activation . Dong G. Springer Verlag; Berlin/Heidelberg: 2014
14b Hoang TT, Dudley GB, Williams LJ. Fragmentation Reactions . In Comprehensive Organic Synthesis II, 2nd ed. Knochel P. Elsevier; Amsterdam: 2014: 842-860
14c Cleavage of Carbon–Carbon Single Bonds by Transition Metals. Murakami M, Chatani N. Wiley-VCH; Weinheim: 2016
14d Special issue on Carbon–Carbon Bond Cleavage in Stereoselective Synthesis: Marek I. Ed. Chem. Rev.. 2021. 121. 1-561

For reviews on radical-based C–C cleavage reactions, see:

14e Wu X, Zhu C. Chin. J. Chem. 2019; 37: 171
14f Sivaguru P, Wang Z, Zanoni G, Bi X. Chem. Soc. Rev. 2019; 48: 2615
14g Morcillo SP. Angew. Chem. Int. Ed. 2019; 58: 14040

15 Kim D, Zhu Y, Harada S, Aguilar I, Cuomo AE, Wang M, Newhouse T. J. Am. Chem. Soc. 2023; 145: 4394
16 Ji J, Chen J, Qin S, Li W, Zhao J, Li J, Song H, Liu X.-Y, Qin Y. J. Am. Chem. Soc. 2023; 145: 3903
17 Brodie BC. Phil. Trans. R. Soc. 1862; 152: 837
18 Brodie BC. J. Chem. Soc. 1864; 17: 266
19 Parnell J. J. Chem. Soc. 1868; 21: 356
20 Fenton HJ. H. J. Chem. Soc., Trans. 1894; 65: 899
21 Haber F, Weiss J. Naturwissenschaften 1932; 20: 948
22 George P, Walsh AD. Trans. Faraday Soc. 1946; 42: 94
23 Wieland H, Maier J. Ber. Dtsch. Chem. Ges. (A and B Series). 1931; 64: 1205

For historical examples of radical decarboxylation from acyl peroxides, see :

24a Gelissen H, Hermans PH. Ber. Dtsch. Chem. Ges. (A and B Series) 1925; 58: 476
24b Overhoff J, Tilman G. Rec. Trav. Chim. Pays-Bas 1929; 48: 993
24c Hey DH. J. Chem. Soc. (Resumed) 1934; 1966
24d Hey DH, Waters WA. Chem. Rev. 1937; 21: 169
24e Walker OJ, Wild GL. E. J. Chem. Soc. (Resumed) 1937; 1132
24f Kharasch MS, Kane SS, Brown HC. J. Am. Chem. Soc. 1941; 63: 526
24g Kharasch MS, Rowe JL, Urry WH. J. Org. Chem. 1951; 16: 905
24h Kharasch MS, Kuderna J, Nudenberg W. J. Org. Chem. 1954; 19: 1283
24i Greene FD. J. Am. Chem. Soc. 1955; 77: 4869
24j Greene FD, Stein HP, Chu CC, Vane FM. J. Am. Chem. Soc. 1964; 86: 2080

For recent examples of radical decarboxylation reactions from peroxides, see:

25a Yu F, Wang T, Zhou H, Li Y, Zhang X, Bao H. Org. Lett. 2017; 19: 6538
25b Cui Z, Du D.-M. J. Org. Chem. 2018; 83: 5149
25c Deng W, Feng W, Li Y, Bao H. Org. Lett. 2018; 20: 4245
25d Ge L, Wujun J, Zhou H, Chen S, Ye C, Yu F, Qian B, Li Y, Bao H. Chem. Asian J. 2018; 13: 2522
25e Kawamura S, Henderson C, Aoki Y, Sekine D, Kobayashi S, Sodeoka M. Chem. Commun. 2018; 54: 11276
25f Ye C, Qian B, Li Y, Su M, Li D, Bao H. Org. Lett. 2018; 20: 3202
25g Ye C, Li Y, Zhu X, Hu S, Yuan D, Bao H. Chem. Sci. 2019; 10: 3632
25h Zhu X, Deng W, Chiou M.-F, Ye C, Jian W, Zeng Y, Jiao Y, Ge L, Li Y, Zhang X, Bao H. J. Am. Chem. Soc. 2019; 141: 548
25i Wei R, Xiong H, Ye C, Bao H. Org. Lett. 2020; 22: 3195
25j Zhu X, Su M, Zhang Q, Li Y, Bao H. Org. Lett. 2020; 22: 620
25k Aoki Y, Kawamura S, Sodeoka M. Org. Synth. 2021; 98: 84
25l Tagami T, Aoki Y, Kawamura S, Sodeoka M. Org. Biomol. Chem. 2021; 19: 9148
25m Tang Z.-L, Ouyang X.-H, Song R.-J, Li J.-H. Org. Lett. 2021; 23: 1000
25n Wang K, Li Y, Li X, Li D, Bao H. Org. Lett. 2021; 23: 8847
25o Zhu X, Jian W, Huang M, Li D, Li Y, Zhang X, Bao H. Nat. Commun. 2021; 12: 6670

26 Hartmann M, Seiberth M. Helv. Chim. Acta 1932; 15: 1390
27 Wieland H, Chromeztka F. Ber. Dtsch. Chem. Ges. (A and B Series) 1930; 63: 1028
28 See the series titled Studies in Organic Peroxides. First publication: Milas NA, Harris SA. J. Am. Chem. Soc. 1933; 55: 349
29 Milas NA, Surgenor DM. J. Am. Chem. Soc. 1946; 68: 205
30 See the series titled Decompositions of Di-t-Alkyl Peroxides. First publication: Raley JH, Rust FF, Vaughan WE. J. Am. Chem. Soc. 1948; 70: 88
31 See the series titled Reactions of Organic Peroxides. First publication: Hawkins EG. E. J. Chem. Soc. 1949; 2076
32 Hawkins EG. E, Young DP. J. Chem. Soc. 1950; 2804
33 See the series titled The Chemistry of Hydroperoxides. First publication: Kharasch MS, Fono A, Nudenberg W. J. Org. Chem. 1950; 15: 748
34 Kharasch MS, Fono A. J. Org. Chem. 1959; 24: 606
35 Kharasch MS, Fono A, Nudenberg W. J. Org. Chem. 1950; 15: 763
36 Hawkins EG. E. J. Chem. Soc. 1955; 3463
37 Youngman EA, Rust FF, Coppinger GF, De La Mare HE. J. Org. Chem. 1963; 28: 144
38 Chiusoli GP, Minisci F. Gazz. Chim. Ital. 1958; 88: 261
39 Minisci F, Portolani A. Gazz. Chim. Ital. 1959; 89: 1941
40 Minisci F. Gazz. Chim. Ital. 1959; 89: 2428
41 Minisci F. Gazz. Chim. Ital. 1959; 89: 1910
42 Minisci F, Portolani A. Gazz. Chim. Ital. 1959; 89: 1922
43 Minisci F, Belvedere G. Gazz. Chim. Ital. 1960; 90: 1299
44 Minisci F. Tetrahedron 1970; 26: 4083
45 Kumamoto J, De La Mare HE, Rust FF. J. Am. Chem. Soc. 1960; 82: 1935
46 De La Mare HE, Kochi JK, Rust FF. J. Am. Chem. Soc. 1961; 83: 2013
47 De La Mare HE, Kochi JK, Rust FF. J. Am. Chem. Soc. 1963; 85: 1437
48 Kochi JK, Mains HE. J. Org. Chem. 1965; 6: 1862
49 Dworkin JH, Dehnert BW, Kwon O. Trends Chem. 2023; 5: 174
50 Brodie BC. Justus Liebigs Ann. Chem. 1858; 108: 79
51 Milas NA, Surgenor DM. J. Am. Chem. Soc. 1946; 68: 642
52 Wolffenstein R. Ber. Dtsch. Chem. Ges. 1895; 28: 2265
53 Bach MA. C. R. Hebd. Seances Acad. Sci. 1897; 124: 951
54 Engler C, Wild W. Ber. Dtsch. Chem. Ges. 1897; 30: 1669
55 Milas NA, Harris SA. J. Am. Chem. Soc. 1938; 60: 2434
56 Milas NA, Panagiotakos PC. J. Am. Chem. Soc. 1940; 62: 1878
57 Windaus A, Brunken J. Liebigs Ann. Chem. 1928; 460: 225
58 Bartlett PD, Schaap AP. J. Am. Chem. Soc. 1970; 92: 3223
59 Schenck GO, Eggert H, Denk W. Justus Liebigs Ann. Chem. 1953; 584: 177
60 Schönbein CF. Ber. Verh. Nat. Ges. Basel 1838; 4: 58
61 Criegee R. Justus Liebigs Ann. Chem. 1948; 560: 127
62 Criegee R, Dietrich H. Justus Liebigs Ann. Chem. 1948; 560: 135
63 Criegee R, Schnorrenberg W. Justus Liebigs Ann. Chem. 1948; 560: 141
64 Criegee R, Wenner G. Justus Liebigs Ann. Chem. 1949; 564: 9
65 Isayama S, Mukaiyama T. Chem. Lett. 1989; 18: 573
66 Liu W, Li Y, Liu K, Li Z. J. Am. Chem. Soc. 2011; 133: 10756

For selected examples of difunctionalization featuring peroxidation, see:

67a Cheng J.-K, Loh T.-P. J. Am. Chem. Soc. 2015; 137: 42
67b Shi E, Liu J, Liu C, Shao Y, Wang H, Lv Y, Ji M, Bao X, Wan X. J. Org. Chem. 2016; 81: 5878
67c Cheng J.-K, Shen L, Wu L.-H, Hu X.-H, Loh T.-P. Chem. Commun. 2017; 53: 12830
67d Lan Y, Chang X.-H, Fan P, Shan C.-C, Liu Z.-B, Loh T.-P. Xu Y.-H. 2017; 7: 7120
67e Zhang H.-Y, Ge C, Zhao J, Zhang Y. Org. Lett. 2017; 19: 5260
67f Zhao L, Wang Y, Ma Z, Wang Y. Inorg. Chem. 2017; 56: 8166
67g Chen Y, Ma Y, Li L, Jiang H, Li Z. Org. Lett. 2019; 21: 1480
67h Shen J, Xiao B, Hou Y, Wang X, Li G.-Z, Chen J.-C, Wang W.-L, Cheng J.-B, Yang B, Yang S.-D. Adv. Synth. Catal. 2019; 361: 5198
67i Wu C.-S, Li R, Wang Q.-Q, Yang L. Green Chem. 2019; 21: 269
67j Chen Y, Ma Y, Li L, Cui M, Li Z. Org. Chem. Front. 2020; 7: 1837
67k Wang L, Ma Y, Jiang Y, Lv L, Li Z. Chem. Commun. 2021; 57: 7846
67l Luo Y, Xu B, Lv L, Li Z. Org. Lett. 2022; 24: 2425

68 Wang X.-T, Han W.-B, Chen H.-J, Zha Q, Wu Y. J. Org. Chem. 2020; 85: 10007
69 Bailey PS, Bath SS. J. Am. Chem. Soc. 1957; 79: 3120
70 Uskoković M, Gut M, Dorfman RI. J. Am. Chem. Soc. 1960; 82: 3668
71 Koechlin B, Reichstein T. Helv. Chim. Acta 1944; 27: 549

For examples on the application of Schreiber’s protocol including in total synthesis, see:

72a Jansen BJ. M, Kreuger JA, De Groot A. Tetrahedron 1989; 45: 1447
72b Meulemans TM, Stork GA, Macaev FZ, Jansen BJ. M, de Groot A. J. Org. Chem. 1999; 64: 9178
72c Jiang C.-H, Bhattacharyya A, Sha C.-K. Org. Lett. 2007; 9: 3241
72d Velthuisen EJ, Danishefsky SJ. J. Am. Chem. Soc. 2007; 129: 10640
72e Beaulieu M.-A, Sabot C, Achache N, Guérard KC, Canesi S. Chem. Eur. J. 2010; 16: 11224
72f Gui J, Wang D, Tian W. Angew. Chem. Int. Ed. 2011; 50: 7093
72g Huang D, Schuppe AW, Liang MZ, Newhouse TR. Org. Biomol. Chem. 2016; 14: 6197
72h Schuppe AW, Newhouse TR. J. Am. Chem. Soc. 2017; 139: 631
72i Liffert R, Linden A, Gademann K. J. Am. Chem. Soc. 2017; 139: 16096
72j Manoni F, Rumo C, Li L, Harran PG. J. Am. Chem. Soc. 2018; 140: 1280

73 Henry CE, Xu Q, Fan YC, Martin TJ, Belding L, Dudding T, Kwon O. J. Am. Chem. Soc. 2014; 136: 11890
74 Srikrishna A, Kumar PR, Gharpure SJ. Tetrahedron Lett. 2001; 42: 3929
75 Srikrishna A, Ravi G. Tetrahedron 2008; 64: 2565
76 Srikrishna A, Reddy TJ. Tetrahedron 1998; 54: 11517
77 Pogrebnoi S, Sarabèr FC. E, Jansen BJ. M, de Groot A. Tetrahedron 2006; 62: 1743
78 Denmark SE, Cresswell AJ. J. Org. Chem. 2013; 78: 12593

79a Bowry VW, Ingold KU. J. Am. Chem. Soc. 1992; 114: 4992
79b Chateauneuf J, Lusztyk J, Ingold KU. J. Org. Chem. 1988; 53: 1629
79c Beckwith AJ, Bowry VW, Ingold KU. J. Am. Chem. Soc. 1992; 114: 4983

80 Wu Z, Pratt DA. J. Am. Chem. Soc. 2020; 142: 10284

81a Huston P, Espenson JH, Bakac A. Inorg. Chem. 1992; 31: 720
81b Dénès F, Pichowicz M, Povie G, Renaud P. Chem. Rev. 2014; 114: 2587

82 Wu D, Mei H, Tan P, Lu W, Zhu J, Wang W, Huan J, Li J. Tetrahedron Lett. 2015; 56: 4383
83 Jang J, Sin KS, Park H. Arch. Pharmacal Res. 2001; 24: 503

84a Fischer H. Substituent Effects in Radical Chemistry . Viehe HG, Janousek Z, Merenyi R. Reidel; Dordrecht: 1986: 123-142
84b Wong MW, Radom L. J. Phys. Chem. 1995; 99: 8582
84c Zytowski T, Fischer H. J. Am. Chem. Soc. 1996; 118: 437
84d Rubin H, Fischer H. Helv. Chim. Acta 1996; 79: 1670
84e Fischer H, Radom L. Angew. Chem. Int. Ed. 2001; 40: 1340
84f Newcomb M. Radical Kinetics and Clocks, In Encyclopedia of Radicals in Chemistry, Biology and Materials . Chatgilialoglu C, Studer A. John Wiley & Sons; Chichester: 2012: 107-124
84g Wille U. Chem. Rev. 2013; 113: 813