Reaction of Linear Push-Pull Enamines at the β′-Position

Aleksandr N. Kostyuk; Dmitriy M. Volochnyuk; Dmitriy A. Sibgatulin

doi:10.1055/s-2007-1000848

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synthesis 2008(2): 161-184
DOI: 10.1055/s-2007-1000848

REVIEW

Reaction of Linear Push-Pull Enamines at the β′-Position

Aleksandr N. Kostyuk*, Dmitriy M. Volochnyuk, Dmitriy A. Sibgatulin
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska 5, Kyiv-94 02094, Ukraine
Fax: +380(44)5373253; e-Mail: a.kostyuk@enamine.net;

Further Information

Publication History

Received 30 July 2007
Publication Date:
18 December 2007 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Enamine tautomerism is often the main cause of regioselectivity problems in the chemistry of enamines derived from ketones. Linear push-pull tertiary enamines featuring a methyl (methylene) group at the α-position do not experience such tautomerism; nevertheless, a number of reactions proceed with participation of the methyl (methylene) group. It was our objective to analyze all known reactions of this type and show their high synthetic potential.

1 Introduction

2 Electrophilic Functionalization of Preformed Lithiated or Silylated Enamines

3 Uncatalyzed Reactions of Monoelectrophilic Reagents at the Methyl (Methylene) Group

4 Reactions Proceeding at Both the β- and β′-Carbon of the Enamine

5 Reactions Proceeding at the α-Methyl (Methylene) Group and β-Functional Group

6 Conclusion

Key words

push-pull enamines - electrophilic functionalizations - cyclization - 1,3-binucleophiles

References

1a The Chemistry of Enamines Rappoport Z. Wiley; Chichester: 1994.

Google Scholar
1b Enamines: Synthesis, Structure and Reactions Cook AG. Marcel Dekker; New York: 1988.

Google Scholar
9 Schlessinger RH. Poss MA. J. Am. Chem. Soc. 1982, 104: 357

Crossref Google Scholar
13 Schlessinger RH. Poss MA. Richardson S. J. Am. Chem. Soc. 1986, 108: 3112

Crossref Google Scholar
14 Schlessinger RH. Li Y.-J. J. Am. Chem. Soc. 1996, 118: 3301

Crossref Google Scholar
18 Schlessinger RH. Gillman KW. Tetrahedron Lett. 1996, 37: 1331

Crossref Google Scholar
19 Schlessinger RH. Gillman KW. Tetrahedron Lett. 1999, 40: 1257

Google Scholar
2 Yoshimoto M. Ishida N. Hiraoka T. Tetrahedron Lett. 1973, 39

Crossref Google Scholar
3 Chan TH. Kang GJ. Tetrahedron Lett. 1982, 23: 3011

Crossref Google Scholar
4 Kang GJ. Chan TH. Can. J. Chem. 1985, 63: 3102

Crossref Google Scholar
5 Dugger RW. Heathcock CH. J. Org. Chem. 1980, 45: 1181

Crossref Google Scholar
6 Williard PG. Tata JR. Schlessinger RH. Adams AD. Iwanowicz EJ. J. Am. Chem. Soc. 1988, 110: 7901

Crossref Google Scholar
7 Adams AD. Schlessinger RH. Tata JA. Venit JJ. J. Org. Chem. 1986, 51: 3068

Crossref Google Scholar
8a Cram DJ. Elhafez FG. J. Am. Chem. Soc. 1952, 74: 5828

Crossref Google Scholar
8b Cram DJ. Wilson DR. J. Am. Chem. Soc. 1963, 85: 1245

Crossref Google Scholar
10 Schlessinger RH. Iwanowicz EJ. Springer JP. J. Org. Chem. 1986, 51: 3070

Crossref Google Scholar
11 Fray MJ. Thomas EJ. J. Chem. Soc., Perkin Trans. 1 1985, 2763

Crossref Google Scholar
12 Schlessinger RH. Bebernitz GR. Lin P. J. Am. Chem. Soc. 1985, 107: 1777

Crossref Google Scholar
15 Dankwardt JW. Dankwardt SM. Schlessinger RH. Tetrahedron Lett. 1998, 39: 4983

Crossref Google Scholar
16 Whitesell JK. Minton MA. Chen K.-M. J. Org. Chem. 1988, 53: 5383

Crossref Google Scholar
17 Schlessinger RH. Li Y.-J. Von Langen DJ. J. Org. Chem. 1996, 61: 3226

Crossref Google Scholar
20 Schlessinger RH. Pettus LH. J. Org. Chem. 1998, 63: 9089

Crossref Google Scholar
21 Schlessinger RH. Tata JR. Springer JP. Tetrahedron Lett. 1987, 28: 5423

Crossref Google Scholar
22 Schlessinger RH. Tata JR. Springer JP. J. Org. Chem. 1987, 52: 708

Crossref Google Scholar
23 Schlessinger RH. Lin P. Poss M. Heterocycles 1987, 25: 315

Crossref Google Scholar
24 Li Y.-J. Liu Z.-T. Yang S.-C. Tetrahedron Lett. 2001, 42: 8011

Crossref Google Scholar
25 Lyubchanskaya VM. Muhanova TI. Alekseeva LM. Granik VG. Khim.-Farm. Zh. 1995, 29: 37

Google Scholar
26 Vereshchagin LI. Gavrilov LD. Bolshedvorskaya RL. Kirillova LP. Ohapkina LL. Zh. Org. Khim. 1973, 9: 506

Google Scholar
27 Satyanarayana J. Reddy KR. Ila H. Janjappa H. Tetrahedron Lett. 1992, 33: 6173

Crossref Google Scholar
28 Reddy KR. Ila H. Janjappa H. Synthesis 1995, 929

Article in Thieme Connect Google Scholar
29 Gravel D. Labelle M. Can. J. Chem. 1985, 63: 1874

Crossref Google Scholar
30 Greaves PM. Landor SR. Chem. Commun. 1966, 322

Google Scholar
31 Fomum ZT. Greaves PM. Landor PD. Landor SR. J. Chem. Soc., Perkin Trans. 1 1973, 1108

Crossref Google Scholar
32 Bestmann HJ. Graf G. Hartung H. Kolewa S. Vilsmaier E. Chem. Ber. 1970, 103: 2794

Crossref Google Scholar
33 Yoshimoto M. Hiraoka T. Kishida Y. Chem. Pharm. Bull. 1970, 18: 2469

Crossref Google Scholar
34 Boehme H. Willinger G. Arch. Pharm. Ber. Dtsch. Pharm. Ges. 1969, 974

Google Scholar
35 Volochnyuk DM. Kostyuk AN. Sibgatulin DA. Petrenko AE. Synthesis 2004, 2545

Article in Thieme Connect Google Scholar
36 Sibgatulin DA. Volochnyuk DM. Kostyuk AN. Synlett 2005, 1904

Google Scholar
37 Sibgatulin DA. Volochnyuk DM. Kostyuk AN. Tetrahedron Lett. 2007, 48: 2775

Crossref Google Scholar
38a
Volochnyuk, D. M.; Kostyuk, A. N.; Sibgatulin, D. A.; Vovk, M. V.; Tolmachev, A. A.; Pinchuk, A. M. Abstracts of Papers, 14th European Symposium on Fluorine Chemistry, Poznan, Poland, July 11-16, 2004; Abstract AO-04.
38b
Sibgatulin, D. A.; Volochnyuk, D. M.; Kostyuk, A. N. Abstracts of Papers, 7th All-Russian Conference, Fluorine Chemistry, Moscow, Russian Federation, June 5-9, 2006; Abstract P-45.
39 Moehrle H. Reinhardt HW. Arch. Pharm. (Weinheim Ger.) 1984, 317: 1017

Crossref Google Scholar
40 Moehrle H. Reinhardt HW. Arch. Pharm. (Weinheim Ger.) 1984, 317: 156

Crossref Google Scholar
41 Sibgatulin DA. Volochnyuk DM. Rusanov EB. Kostyuk AN. Synthesis 2006, 1625

Article in Thieme Connect Google Scholar
42 Burger K. Hein F. Liebigs Ann. Chem. 1982, 853

Crossref Google Scholar
43 Boehme H. Traenka M. Liebigs Ann. Chem. 1985, 149

Crossref Google Scholar
44 Alt GH. Speziale AJ. J. Org. Chem. 1964, 29: 798

Crossref Google Scholar
45 Alt GH. Speziale AJ. J. Org. Chem. 1964, 29: 795

Google Scholar
46 Helmers R. Tetrahedron Lett. 1966, 1905

Crossref Google Scholar
47 Jacquier R. Maurey G. Bull. Soc. Chim. Fr. 1967, 320

Google Scholar
48 Kostyuk AN. Svyaschenko YV. Volochnyuk DM. Lysenko NV. Tolmachev AA. Pinchuk AM. Tetrahedron Lett. 2003, 6487

Crossref Google Scholar
49 Van den Goorberg JAM. Van der Gen A. Tetrahedron Lett. 1980, 21: 3621

Crossref Google Scholar
50 Woodward RB. Pachter IJ. Scheinbaum ML. J. Org. Chem. 1971, 36: 1137

Crossref Google Scholar
51 Woodward RE, and Bickel H. inventors; US Patent 4550162.
52 Lauer WM. Cromwell NH. J. Am. Chem. Soc. 1942, 64: 612

Crossref Google Scholar
53 Rao RB. Sing UP. Bhide GV. Tetrahedron Lett. 1967, 719

Crossref Google Scholar
54 Tsuge O. Inaba A. Bull. Chem. Soc. Jpn. 1973, 46: 286

Crossref Google Scholar
55 Simunek P. Bertolasi V. Lycka A. Machacek V. Org. Biomol. Chem. 2003, 1: 3250

Crossref Google Scholar
56 Granik VG. Grizik SI. Solov’eva NP. Anisimova OS. Sheiker YuN. Russ. J. Org. Chem. (Engl. Transl.) 1984, 20: 673

Google Scholar
57 Camps P. Jaime C. Molas J. Tetrahedron Lett. 1981, 22: 2487

Crossref Google Scholar
58 Node M. Fujiwara T. Ichihashi S. Nishide K. Tetrahedron Lett. 1998, 39: 6331

Crossref Google Scholar
59 Auricchio S. Bernardi R. Ricca A. Tetrahedron Lett. 1976, 4831

Crossref Google Scholar
60 Boehme H. Traenka M. Liebigs Ann. Chem. 1985, 485

Crossref Google Scholar
61 Kashima C. Yamamoto Y. J. Heterocycl. Chem. 1980, 17: 1141

Crossref Google Scholar
62 Boehme H. Graetzel von Graetz J. Martin F. Matusch R. Nehne J. Liebigs Ann. Chem. 1980, 394

Crossref Google Scholar
63a Harris RLN. Huppatz JL. Phillips JN. Angew. Chem. 1976, 88: 539

Crossref Google Scholar
63b Harris RLN. Huppatz JL. Phillips JN. Aust. J. Chem. 1977, 30: 2213

Crossref Google Scholar
64 Volochnyuk DM. Kostyuk AN. Sibgatulin DA. Chernega AN. Tetrahedron 2005, 61: 2839

Crossref Google Scholar
65 Volochnyuk DM. Kostyuk AN. Sibgatulin DA. Chernega AN. Pinchuk AM. Tolmachev AA. Tetrahedron 2004, 60: 2361

Crossref Google Scholar
66 Chkanikov ND. In Enamines in Organic Synthesis (in Russian) UO RAN; Ekaterenburg: 2001. p.108-120

Google Scholar
67 Hickmott PW. Sheppard G. J. Chem. Soc., Perkin Trans. 1 1972, 1038

Crossref Google Scholar
68 Belyaeva OY. Granik VG. Glushkov RG. Vlasova TF. Anisimova OS. Chem. Heterocycl. Compd. (Engl. Transl.) 1978, 14: 653

Crossref Google Scholar
69 Lyubchanskaya VM. Sarisova LS. Alekseeva LM. Granik VG. Khim.-Farm. Zh. 1994, 49

Google Scholar
70 Nitta H. Takimoto K. Ueda I. Chem. Pharm. Bull. 1992, 40: 858

Crossref Google Scholar
71 Take K. Okumura K. Takimoto K. Kato M. Ohtsuka M. Shiokawa Y. Chem. Pharm. Bull. 1991, 39: 2915

Crossref Google Scholar
72 Goerlitzer K. Trittmacher J. Jones PG. Frohberg P. Drutkowsi G. Pharmazie 2003, 58: 776

Google Scholar
73 Michael JP. Howard AS. Katz RB. Zwane MI. Tetrahedron Lett. 1992, 4751

Crossref Google Scholar
74 Singh H. Dolly Hundal MS. Hundal G. Singh P. Singh Chimni S. Kumar S. Tetrahedron 1998, 54: 7563

Crossref Google Scholar
75 Tsuge O. Inaba A. Heterocycles 1975, 3: 1081

Crossref Google Scholar
76 Tsuge O. Inaba A. Bull. Chem. Soc. Jpn. 1976, 49: 2828

Crossref Google Scholar
77 Volochnyuk DM. Kostyuk AN. Bol’but AV. Sibgatulin DA. Kuklya AS. Vovk MV. Synthesis 2004, 2196

Article in Thieme Connect Google Scholar
78a Gromov SP. Yashunskii DV. Sagitullin RS. Bundel YuG. Dokl. Chem. (Engl. Transl.) 1987, 292: 12

Google Scholar
78b Gromov SP, Yashunskii DV, Sagitullin RS, and Kost AN. inventors; SU Patent 1049484. ; Chem. Abstr. 1984, 100, 120898
79 Gompper R. Heinemann U. Angew. Chem. 1980, 92: 207

Crossref Google Scholar
80 Kostyuk AN. Svyaschenko YV. Volochnyuk DM. Tetrahedron 2005, 61: 9263

Crossref Google Scholar
81 Svyaschenko YV. Barnich BB. Kostyuk AN. Volochnyuk DM. Tetrahedron 2007, 63: 5656

Crossref Google Scholar
82 Kostyuk AN. Svyaschenko YV. Volochnyuk DM. In Nitrogen-Containing Heterocycles Vol. 2: Kartsev VG. ICSPF Press; Moscow: 2006. p.322-323

Google Scholar
83 Tsuge O. Inaba A. Bull. Chem. Soc. Jpn. 1973, 46: 2221

Crossref Google Scholar
84 Burger K. Wassmuth U. Hein F. Rottegger S. Liebigs Ann. Chem. 1984, 991

Crossref Google Scholar
85a Akhrem AA. Chernov YuG. Synthesis 1980, 996

Google Scholar
85b Akhrem AA. Chernov YuG. Dokl. Chem. (Engl. Transl.) 1980, 255: 865

Google Scholar
86 Holy A. Arnold Z. Collect. Czech. Chem. Commun. 1965, 53

Google Scholar