Abstract
Guanidine is categorized as an organic superbase, yet its synthetic application is immature despite its wide potential utility. The role of guanidine in organic synthesis, including asymmetric reactions, is discussed herein.
1 Introduction
2 TMG and Its Analogues in Organic Synthesis
2.1 Alkylation of Carboxylic Acids
2.2 Barton’s Bases
2.3 Baylis-Hillman Reactions
2.4 Bismuth-Mediated Reactions
2.5 Cyclopropanations
2.6 Horner-Emmons Reactions
2.7 Ionic Liquids
2.8 Michael Reactions
2.9 Nitroaldol (Henry) Reactions
2.10 Nucleophilic Reactions with Thiols
2.11 Palladium-Catalyzed Reactions
2.12 Silylation of Alcohols
2.13 Supported Guanidines
2.14 TMG Azides
3 Applications toward Asymmetric Synthesis
3.1 Alkylation of Carboxylic Acids
3.2 Alkylation of Schiff Bases
3.3 Azidations
3.4 Michael Reactions
3.5 Nitroaldol (Henry) Reactions
3.6 Nucleophilic Epoxidations
3.7 Silylation of Alcohols
3.8 Strecker Reactions
3.9 TMS Cyanations
3.10 Others
4 Conclusion
Key words
catalysis - asymmetric synthesis - chiral auxiliary - guanidine - organic base
References
1a
Costa M.
Chiusoli GP.
Taffurelli D.
Dalmonego G.
J. Chem. Soc., Perkin Trans. 1
1998,
1541
1b
Kovacevic B.
Maksic ZB.
Org. Lett.
2001,
3:
1523
2
Yamamoto Y.
Kojima S.
The Chemistry of Amidines and Imidates
Vol. 2:
Patai S.
Rappoport Z.
John Wiley & Sons Inc.;
New York:
1991.
p.485-526
3a
Isobe T.
Fukuda K.
Ishikawa T.
J. Org. Chem.
2000,
65:
7770
3b
Isobe T.
Fukuda K.
Tokunaga T.
Seki H.
Yamaguchi K.
Ishikawa T.
J. Org. Chem.
2000,
65:
7774
3c
Isobe T.
Fukuda K.
Yamaguchi K.
Seki H.
Tokunaga T.
Ishikawa T.
J. Org. Chem.
2000,
65:
7779
4
Ishikawa T.
Isobe T.
Chem. Eur. J.
2002,
8:
552
5
Schenck M.
Hoppe-Seyler’s Z. Physiol. Chem.
1912,
77:
370
6
Schenck M.
von Graevenitz F.
Hoppe-Seyler’s Z. Physiol. Chem.
1924,
141:
139-144
7a
Tanaka K.
Kamatani M.
Mori H.
Fujii S.
Ikeda K.
Hisada M.
Itagaki Y.
Katsumura S.
Tetrahedron Lett.
1998,
39:
1185
7b
Kocienski PJ.
Brown RCD.
Pommier A.
Procter M.
Schmidt B.
J. Chem. Soc., Perkin Trans. 1
1998,
9
8a
Barton DHR.
Elliott JD.
Gero SD.
J. Chem. Soc., Chem. Commun.
1981,
1136
8b
Barton DHR.
Elliott JD.
Gero SD.
J. Chem. Soc., Perkin Trans. 1
1982,
2085
9a
Barton DHR.
Bashiardes G.
Fourrey J.-L.
Tetrahedron Lett.
1983,
24:
1605
9b
Barton DHR.
Chen M.
Jaszberenyi JC.
Taylor DK.
Org. Synth.
1997,
74:
101
10
Furrow ME.
Myers AG.
J. Am. Chem. Soc.
2004,
126:
5436
11a
Wipf P.
Lynch SM.
Org. Lett.
2003,
5:
1155
11b
Wipf P.
Lynch SM.
Birmingham A.
Tamayo G.
Jimenez A.
Campos N.
Powis G.
Org. Biomol. Chem.
2004,
2:
1651
12
Cooper DM.
Grigg R.
Hargreaves S.
Kennewell P.
Redpath J.
Tetrahedron
1995,
51:
7791
13a
Leadbeater NE.
van der Pol C.
J. Chem. Soc., Perkin Trans. 1
2001,
2831
13b
Graunger RS.
Leadbeater NE.
Pamies MA.
Catal. Commun.
2002,
3:
449
14a
Fedorov A.
Combes S.
Finet J.-P.
Tetrahedron
1999,
55:
1341
14b
Matano Y.
Imahori H.
J. Org. Chem.
2004,
69:
5505
15
Anastasia M.
Allevi P.
Ciuffeda P.
Fiecchi A.
Synthesis
1983,
123
16a
Travins JM.
Etzkorn FA.
J. Org. Chem.
1997,
62:
8387
16b
Debenham SD.
Debenham JS.
Burk MJ.
Toone EJ.
J. Am. Chem. Soc.
1997,
119:
9897
16c
Varie DL.
Brennam J.
Briggs B.
Cronin JS.
Hay DA.
Rieck JA.
Zmijewski MJ.
Tetrahedron Lett.
1998,
39:
8405
16d
Ritzen A.
Basu B.
Waellgerg A.
Frejd T.
Tetrahedron: Asymmetry
1998,
9:
3491
17a
Huang J.
Jiang T.
Gao H.
Han B.
Liu Z.
Wu W.
Chang Y.
Zhao G.
Angew. Chem. Int. Ed.
2004,
43:
1397
17b
Yang Y.
Deng C.
Yuan Y.
J. Catal.
2005,
232:
108
17c
Zhu A.
Jiang T.
Wang D.
Han B.
Liu L.
Huang J.
Zhang J.
Sun D.
Green Chem.
2005,
7:
514
17d
Wang P.
Zakeeruddin SM.
Graetzel M.
Kantlehner W.
Mezger J.
Stoyanov EV.
Scherr O.
App. Phys. A: Mater. Sci. Process.
2004,
79:
73
18
Nysted LN.
Burtner RR.
J. Org. Chem.
1962,
27:
3175
19a
Pollini GP.
Barco A.
De Giuli G.
Synthesis
1972,
44
19b
Alvarez FS.
Wren D.
Tetrahedron Lett.
1973,
569
19c
Hewson AT.
MacPherson DT.
Tetrahedron Lett.
1983,
24:
647
19d
Naito T.
Honda Y.
Bhavakul V.
Yamaguchi S.
Fujiwara A.
Miyata O.
Ninomiya I.
Chem. Pharm. Bull.
1997,
45:
1932
20
Nagasawa K.
Georgieva A.
Takahashi H.
Nakata T.
Tetrahedron
2001,
57:
8959
21
Simoni D.
Invidiata FP.
Manferdini M.
Lampronti I.
Rondonin R.
Roberti M.
Pollini GP.
Tetrahedron Lett.
1998,
39:
7615
22a
Forsyth AC.
Paton RM.
Watt I.
Tetrahedron Lett.
1989,
30:
993
22b
Hossain N.
Garg N.
Chattopadhyaya J.
Tetrahedron
1993,
49:
10061
23a
Xia Y.
Kozikowski AP.
J. Am. Chem. Soc.
1989,
111:
4116
23b
Kozikowski AP.
Prakash KRC.
Saxena A.
Doctor BP.
Chem. Commun.
1998,
1287
24
Simoni D.
Invidiata FP.
Manfredini S.
Ferroni R.
Lampronti I.
Roberti M.
Pollini GP.
Tetrahedron Lett.
1997,
38:
2749
25a
Hossain N.
Herdewijn P.
Nucleosides Nucleotides
1998,
17:
1781
25b
Hossain N.
van Halbeek H.
De Clercq E.
Herdewijn P.
Tetrahedron
1998,
54:
2209
25c
Ishikawa T.
Shimizu Y.
Kudoh T.
Saito S.
Org. Lett.
2003,
5:
3879
26
Bernardi L.
Bonini BF.
Capito E.
Dessole G.
Comes-Franchini M.
Fochi M.
Ricci A.
J. Org. Chem.
2004,
69:
8168
27a
Van Aken E.
Wynberg H.
Van Bolhuis F.
J. Chem. Soc., Chem. Commun.
1992,
629
27b
Van Aken E.
Wynberg H.
Van Bolhuis F.
Acta Chem. Scand.
1993,
47:
122
28
Bera S.
Langley GJ.
Pathak T.
J. Org. Chem.
1998,
63:
1754
29
Williams JM.
Brands KMJ.
Skerlj RT.
Jobson RB.
Marchesini G.
Conrad KM.
Pipik B.
Savary KA.
Tsay F.-R.
Houghton PG.
Sidler DR.
Dolling U.-H.
DiMichele LM.
Novak TJ.
J. Org. Chem.
2005,
70:
7479
30
Luzzio FA.
Mayorov AV.
Synlett
2003,
532
31
Li S.
Xie H.
Zhang S.
Lin Y.
Xu J.
Cao J.
Synlett
2005,
1885
32
Kim S.
Chang H.
Synth. Commun.
1984,
14:
899
33
Macquarrie DJ.
Modoe JEG.
Brunel D.
Renard G.
Blanc A. In Supported Catalysts and their Applications
Sherrington DC.
Kybett AP.
Royal Society of Chemistry;
Cambridge UK:
2001.
p.196
34a
Sercheli R.
Vargas RM.
Sheldon RA.
Schuchardt U.
J. Mol. Catal. A: Chem.
1999,
148:
173
34b
Blanc AC.
Valle S.
Renard G.
Brunel D.
Macquarrie DJ.
Quinn CR.
Green Chem.
2000,
2:
283
34c
Simoni D.
Rondanin R.
Morini M.
Baruchello R.
Invidiata GP.
Tetrahedron Lett.
2000,
41:
1607
34d
Macquarrie DJ.
Utting KA.
Brunel D.
Renard G.
Blanc A.
Stud. Surf. Sci. Catal.
2002,
142B:
1473
34e
Kim K.-S.
Song JH.
Kim J.-H.
Seo G.
Stud. Surf. Sci. Catal.
2003,
146:
505
34f
Jerome F.
Kharchafi G.
Adam I.
Barrault J.
Green Chem.
2004,
6:
72
35
Papa AJ.
J. Org. Chem.
1966,
31:
1426
36
Xiao D.
Carroll PJ.
Mayer SC.
Pfizenmayer AJ.
Joullie MM.
Tetrahedron: Asymmetry
1997,
8:
3043
37a
Evans DA.
Ellman JA.
Dorow RL.
Tetrahedron Lett.
1987,
28:
1123
37b
Evans DA.
Britton TC.
Ellman JA.
Dorow RL.
J. Am. Chem. Soc.
1990,
112:
4011
37c
Stone MJ.
Maplestone RA.
Rahman SK.
Williams DH.
Tetrahedron Lett.
1991,
32:
2663
37d
Boteju LW.
Wegner K.
Hruby V.
Tetrahedron Lett.
1992,
33:
7491
37e
Dharanipragada R.
VanHulle K.
Bannister A.
Bear S.
Kennedy L.
Hruby VJ.
Tetrahedron
1992,
48:
4733
37f
Davis AP.
Orchard MG.
J. Chem. Soc., Perkin Trans. 1
1993,
919
37g
Larsson U.
Carison R.
Leroy J.
Acta Chem. Scand.
1993,
47:
380
37h
Li C.
Arasappan A.
Fuchs PL.
Tetrahedron Lett.
1993,
34:
3535
37i
Li C.
Shih T.-L.
Jeong JU.
Arasappan A.
Fuchs PL.
Tetrahedron Lett.
1994,
35:
2645
37j
Palacios F.
Aparicio D.
de los Santos JM.
Perez de Heredia I.
Rubiales G.
Org. Prep. Proced. Int.
1995,
27:
171
37k
Crotti P.
Di Bussolo V.
Favero L.
Macchia F.
Pineschi M.
Tetrahedron Lett.
1996,
37:
1675
37l
Radel PA.
Kahl SB.
J. Org. Chem.
1996,
61:
4582
37m
Liao S.
Shenderovich MD.
Lin J.
Hruby VJ.
Tetrahedron
1997,
53:
16645
37n
Bhattarai KM.
Davis AP.
Perry JJ.
Walter CJ.
Menzer S.
Williams DJ.
J. Org. Chem.
1997,
62:
8463
37o
LeMerrer Y.
Gravier-Pelletier C.
Gerrouache M.
Depezay J.-C.
Tetrahedron Lett.
1998,
39:
385
37p
Kinugasa M.
Harada T.
Oku A.
Tetrahedron Lett.
1998,
39:
4529
37q
Gibson CL.
Gillon K.
Cook S.
Tetrahedron Lett.
1998,
39:
6733
37r
Hentemann M.
Fuchs PL.
Tetrahedron Lett.
1999,
40:
2699
37s
Ballereau S.
McCort I.
Dureault A.
Depezay J.-C.
Tetrahedron
2001,
57:
1935
37t
Denmark SE.
Dorow RL.
Chirality
2002,
14:
241
37u
Smith RJ.
Bienz S.
Helv. Chim. Acta
2004,
87:
1681
37v
Di Bussolo V.
Caselli M.
Romano MR.
Pineschi M.
Crotti P.
J. Org. Chem.
2004,
69:
8702
37w
Treweeke NR.
Hitchcock PB.
Pardoe DA.
Caddick S.
Chem. Commun.
2005,
1868
37x
Fotsing JR.
Hagedon M.
Banert K.
Tetrahedron
2005,
61:
8904
38a
Chinchilla R.
Najera C.
Sanchez-Agullo P.
Tetrahedron: Asymmetry
1994,
5:
1393
38b
Ma C.
Cheng K.
Tetrahedron: Asymmetry
1999,
10:
713
39a
Davis AP.
Dempsey KJ.
Tetrahedron: Asymmetry
1995,
6:
2829
39b
Corey EJ.
Grogan MJ.
Org. Lett.
1999,
1:
157
40
Iyer MS.
Gigstad KM.
Namdev ND.
Lipton M.
J. Am. Chem. Soc.
1996,
118:
4910
41a
Howard-Jones A.
Murphy PJ.
Thomas DA.
Caulkett PWR.
J. Org. Chem.
1999,
64:
1039
41b
Kita T.
Georgieva A.
Hashimoto Y.
Nakata T.
Nagasawa K.
Angew. Chem. Int. Ed.
2002,
41:
2832
41c
Allingham MT.
Howard-Jones A.
Murphy PJ.
Thomas DA.
Caulkett PWR.
Tetrahedron Lett.
2003,
44:
8677
42a
Isobe T.
Ishikawa T.
J. Org. Chem.
1999,
64:
5832
42b
Isobe T.
Ishikawa T.
J. Org. Chem.
1999,
64:
6984
42c
Isobe T.
Ishikawa T.
J. Org. Chem.
1999,
64:
6989
42d
Merck Index
13th ed.:
Merck Publishing;
New Jersey:
2001.
p.596
43
Isobe T.
Fukuda K.
Ishikawa T.
Tetrahedron: Asymmetry
1998,
9:
1729
44 sobe, T.; Fukuda, K.; Ishikawa, T. unpublished results
45
Kitani Y.
Kumamoto T.
Isobe T.
Fukuda K.
Ishikawa T.
Adv. Synth. Catal.
2005,
347:
1653
46a
Alcazar V.
Moran JR.
de Mendoza J.
Tetrahedron Lett.
1995,
36:
3941
46b
Martin-Portugues M.
Alcazar V.
Prados P.
de Mendoza J.
Tetrahedron
2002,
58:
2951
46c For the preparation of the related guanidines, see: Echavarren A.
Galan A.
de Mendoza J.
Salmeron A.
Helv. Chim. Acta
1988,
71:
685
46d
Gleich A.
Schmidtchen FP.
Chem. Ber.
1990,
123:
907
47
Ishikawa T.
Araki Y.
Kumamoto T.
Seki H.
Fukuda K.
Isobe T.
Chem. Commun.
2001,
245
For examples, see:
48a
Metzger JO.
Angew. Chem. Int. Ed.
1998,
37:
2975
48b
Tanaka K.
Toda F.
Chem. Rev.
2000,
100:
1025
48c
Aggarwal VK.
Mereu A.
Chem. Commun.
2000,
2310
49
Kumamoto T.
Ebine K.
Endo M.
Araki Y.
Fushimi Y.
Miyamoto I.
Ishikawa T.
Isobe T.
Fukuda K.
Heterocycles
2005,
66:
347 ; some related results are as of yet unpublished
50
Pan Q.-B.
Ma D.-W.
Chin. J. Chem.
2003,
21:
793
51
Isobe T.
Fukuda K.
Araki Y.
Ishikawa T.
Chem. Commun.
2001,
243
52
Groeger H.
Chem. Rev.
2003,
103:
2795
53
Li J.
Jiang W.-Y.
Han K.-L.
He G.-Z.
Li C.
J. Org. Chem.
2003,
68:
8786
54
Hada K.
Watanabe T.
Isobe T.
Ishikawa T.
J. Am. Chem. Soc.
2001,
123:
7705 ; this work was also covered in Chem. Eng. News 2001, Aug. 13, 32
55
Wannaporn D.
Ishikawa T.
J. Org. Chem.
2005,
70:
9399
56 With regard to the guanidinium ylide from N-fluorenyl-guanidinium iodide, see: Lloyd D.
Millar RW.
J. Chem. Soc., Chem. Commun.
1976,
266
57
Haga T.
Ishikawa T.
Tetrahedron
2005,
61:
2857
58
Trost BM.
Yasukata T.
J. Am. Chem. Soc.
2001,
123:
7162
59
Hjelmencrantz A.
Berg U.
J. Org. Chem.
2002,
67:
3585
60a
Koehn U.
Guenther W.
Goerls H.
Anders E.
Tetrahedron: Asymmetry
2004,
15:
1419
60b
Koehn U.
Schulz M.
Goerls H.
Anders E.
Tetrahedron: Asymmetry
2005,
16:
2125