Recent Advances in the Direct Nucleophilic Substitution of Allylic Alcohols through SN1-Type Reactions

Alejandro Baeza; Carmen Nájera

doi:10.1055/s-0033-1340316

Synthesis, Inhaltsverzeichnis

Synthesis 2014; 46(01): 25-34
DOI: 10.1055/s-0033-1340316

short review

Recent Advances in the Direct Nucleophilic Substitution of Allylic Alcohols through S_N1-Type Reactions

Autor*innen

Alejandro Baeza*

Departamento de Química Orgánica and Instituto de Síntesis Orgánica, University of Alicante, Apdo.99, 03080, Alicante, Spain Fax: +34(965)903549 eMail: alex.baeza@ua.es eMail: cnajera@ua.es
Carmen Nájera*

Departamento de Química Orgánica and Instituto de Síntesis Orgánica, University of Alicante, Apdo.99, 03080, Alicante, Spain Fax: +34(965)903549 eMail: alex.baeza@ua.es eMail: cnajera@ua.es

Abstract

Alle Artikel dieser Rubrik

Abstract

Direct nucleophilic substitution reactions of allylic alcohols are environmentally friendly, since they generate only water as a byproduct, allowing access to new allylic compounds. This reaction has, thus, attracted the interest of the chemical community and several strategies have been developed for its successful accomplishment. This review gathers the latest advances in this methodology involving S_N1-type reactions.

1 Introduction

2 S_N1-Type Direct Nucleophilic Substitution Reactions of Allylic Alcohols

2.1 Lewis Acids as Catalysts

2.2 Brønsted Acids as Catalysts

2.3 Other Promoters

3 Conclusions and Outlook

Key words

S_N1 reaction - allylic substitution - carbocations - allylic alcohols - green chemistry

Volltext

Referenzen

References

For recent reviews about the principles of green chemistry, see:

1a Sheldon RA. Chem. Soc. Rev. 2012; 41: 1437
1b Constable DJ. C, Dunn PJ, Hayler JD, Humphrey GR, Leazer Jr JL, Linderman RJ, Lorenz K, Pearlman BA, Wells A, Zaks A, Zhang TY. Green Chem. 2007; 9: 411; and references therein

2 Trost BM. Angew. Chem., Int. Ed. Engl. 1995; 34: 259

For example, see:

3a Paquin J.-F, Lautens M In Comprehensive Asymmetric Catalysis, Supplement 2 . Jacobsen EN, Pfaltz A, Yamamoto H. Springer; Heidelberg: 2004: 73
3b Palladium Reagents and Catalysis . Tsuji J. Wiley; Chichester: 2004
3c Handbook of Organopalladium Chemistry for Organic Systems . Vol. II. Negishi E. Wiley; New York: 2002. Chap. V.2, 1669

For reviews about asymmetric allylic substitutions for example, see:

3d Trost BM, Zhang T, Sieber JD. Chem. Sci. 2010; 1: 427
3e Miyabe H, Takemoto Y. Synlett 2005; 1641
3f Trost BM, Crawley ML. Chem. Rev. 2003; 103: 2921; and references therein

For recent reviews on transition-metal-catalyzed allylic substitution reactions of alcohols, see:

4a Sundararaju B, Achard M, Bruneau C. Chem. Soc. Rev. 2012; 41: 4467
4b Muzart J. Eur. J. Org. Chem. 2007; 3077

5 For recent review on S_N1-type direct nucleophilic substitution of free alcohols, see: Emer E, Sinisi R, Guiteras-Capdevila M, Petruzziello D, De Vincentiis F, Cozzi PG. Eur. J. Org. Chem. 2011; 647

For recent reviews about the use of gold as catalyst in transformations involving alcohols, see:

6a Cera G, Chiarucci M, Bandini M. Pure Appl. Chem. 2012; 84: 1673
6b Biannic B, Aponick A. Eur. J. Org. Chem. 2011; 6605
6c Muzart J. Tetrahedron 2008; 64: 5815

7 Biswas S, Samec JS. M. Chem. Asian. J. 2013; 8: 974
8 Giner X, Trillo P, Nájera C. J. Organomet. Chem. 2011; 696: 357
9 Chen G.-Q, Xu Z.-J, Cahn SL.-F, Zhou C.-Y, Che C.-M. Synlett 2011; 2713
10 Rueping M, Vila C, Uria U. Org. Lett. 2012; 14: 768
11 Ren K, Li P, Wang L, Zhang X. Tetrahedron 2011; 67: 2753
12 Our group, among others, reported the use of cationic gold(I) complexes for the direct amination reaction onto free allylic alcohols (see refs. 6 and 8).
13 Ohshima T, Nakahara Y, Ipposhi J, Miyamoto Y, Mashima K. Chem. Commun. 2011; 47: 8322
14 Ohshima T, Ipposhi J, Nakahara Y, Shibuya R, Mashima K. Adv. Synth. Catal. 2012; 354: 2447
15 Yamamoto H, Ho E, Sasaki I, Mitsutake M, Takagi Y, Imagawa H, Nishizawa M. Eur. J. Org. Chem. 2011; 2417
16 Babu SA, Yasuda M, Tsukahara Y, Yamauchi T, Wada Y, Baba A. Synthesis 2008; 1717
17 Fan G.-P, Liu Z, Wang G.-W. Green Chem. 2013; 15: 1659
18 Theerthagiri P, Lalitha A. Tetrahedron Lett. 2012; 53: 5535
19 Meng B, Ma S. Org. Lett. 2012; 14: 2674
20 Qin H, Yamagiwa N, Matsunaga S, Shibasaki M. Angew. Chem. Int. Ed. 2007; 46: 409

21a Narayana-Kumar GG. K. S, Laali KK. Org. Biomol. Chem. 2012; 10: 7347
21b Aridoss G, Laali KK. Tetrahedron Lett. 2011; 52: 6859

22 Shukla P, Choudhary MK, Nayak SK. Synlett 2011; 1585
23 Das BG, Nallagonda R, Ghorai P. J. Org. Chem. 2012; 77: 5577

Heterobimetallic Sn–Pd complex as catalyst:

24a Das D, Pratihar S, Roy UK, Mal D, Roy S. Org. Biomol. Chem. 2012; 10: 4537

Heterobimetallic Sn–Ir complex as catalyst:

24b Chatterjee PN, Roy S. Tetrahedron 2012; 68: 3776
24c Maity AK, Chatterjee PN, Roy S. Tetrahedron 2013; 69: 942

25a Meyer VJ, Niggemann M. Eur. J. Org. Chem. 2011; 3671
25b Haubenreisser S, Niggemann M. Adv. Synth. Catal. 2011; 353: 469
25c Niggemann M, Meel MJ. Angew. Chem. Int. Ed. 2010; 49: 3684

For a review on the use of Ca(II) as a Lewis Acid catalyst, see:

25d Begouin J.-M, Niggemann M. Chem. Eur. J. 2013; 19: 8030

26 Liu Z, Wang D, Chen Y. Lett. Org. Chem. 2011; 8: 73

27a Li M.-M, Zhang Q, Yue H.-L, Ma L, Ji J.-X. Tetrahedron Lett. 2012; 53: 317

The analogous alkenyl bromides and chlorides were previously reported using 40–50 mol% of the FeBr₃ and FeCl₃, respectively, see:

27b Biswas S, Maiti S, Jana U. Eur. J. Org. Chem. 2009; 2354
27c Liu Z.-Q, Wang J, Han J, Zhao Y, Zhou B. Tetrahedron Lett. 2009; 50: 1240

For intermolecular version, see:

28a Jana U, Biswas S, Maiti S. Tetrahedron Lett. 2007; 48: 4065
28b Jana U, Maiti S, Biswas S. Tetrahedron Lett. 2007; 48: 7160
28c Jana U, Maiti S, Biswas S. Tetrahedron Lett. 2008; 49: 858

For intramolecular version, see:

28d Guérinot A, Serra-Muns A, Gnamm C, Bensoussan C, Reymond S, Cossy J. Org. Lett. 2010; 12: 1808
28e Guérinot A, Serra-Muns A, Bensoussan C, Reymond S, Cossy J. Tetrahedron 2011; 67: 5024

29 Trillo P, Baeza A, Nájera C. Eur. J. Org. Chem. 2012; 2929
30 Trillo P, Baeza A, Nájera C. ChemCatChem 2013; 5: 1538
31 Wang Z, Li S, Yu B, Wu H, Wang Y, Sun X. J. Org. Chem. 2012; 77: 8615
32 Kaper H, Bouchmella K, Mutin PH, Goettmann F. ChemCatChem 2012; 4: 1813

33a Han F, Yang L, Li Z, Xia C. Adv. Synth. Catal. 2012; 354: 1052

The same sulfonic acid functionalized ionic liquids have been successfully employed for the reaction of dicarbonyl compounds with benzylic, allylic, and propargylic alcohols:

33b Funabiki K, Komeda T, Kubota Y, Matsui M. Tetrahedron 2009; 65: 7457

34 Yue H.-L, Wei W, Li M.-M, Yang Y.-R, Ji J.-X. Adv. Synth. Catal. 2011; 353: 3139
35 For example, see: Sanz R, Martínez A, Miguel D, Álvarez-Gutiérrez JM, Rodríguez F. Adv. Synth. Catal. 2006; 348: 1841
36 Reddy CJ, Jithender E, Krishna G, Reddy GV, Jagadeesh B. Org. Biomol. Chem. 2011; 9: 3940
37 Xing C, Sun H, Zhang J, Li G, Chi Y.-R. Chem. Eur. J. 2011; 17: 12272
38 For the asymmetric version of this reaction using alcohols that give highly stabilized carbocations and catalyzed by InBr₃ and imidazolidinone MacMillan’s organocatalyst, see: Guiteras-Capdevila M, Benfatti F, Zoli L, Stenta M, Cozzi PG. Chem. Eur. J. 2010; 16: 11237
39 Zheng Z.-J, Liu L.-X, Gao G, Dong H, Jiang J.-X, Lai G.-Q, Xu L.-W. RSC Adv. 2012; 2: 2895

For the use of H₂SO₄, see:

40a Xia F, Zhao ZL, Liu PN. Tetrahedron Lett. 2012; 53: 2828

For the use of HBF₄, see:

40b Liu PN, Xia F, Ren Y, Chen J. Chin. J. Chem. 2011; 29: 2075

41 Aoyama T, Miyota S, Takido T, Kodomari M. Synlett 2011; 2971
42 For example, see: McCubbin JA, Hosseini H, Krokhin OV. J. Org. Chem. 2010; 75: 959
43 Zheng H, Ghanbari S, Nakamura S, Hall DG. Angew. Chem. Int. Ed. 2012; 51: 6187
44 Wang J, Masui Y, Onaka M. ACS Catal. 2011; 1: 446

For reviews about fluorinated alcohols in organic transformations, see:

45a Begué J.-P, Bonnet-Delpon D, Crousse B. Synlett 2004; 18
45b Shuklov IA, Dubrovina NV, Börner A. Synthesis 2007; 2925

46 Trillo P, Baeza A, Nájera C. J. Org. Chem. 2012; 77: 7344
47 Zhu A, Li L, Wang J, Zhuo K. Green Chem. 2011; 13: 1244

For reviews on the use of allylic alcohols in asymmetric catalysis, see:

48a Bandini M. Angew. Chem. Int. Ed. 2011; 50: 994
48b Bandini M, Cera G, Chiarucci M. Synthesis 2012; 44: 504