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
<A NAME="RE14305SS-1A">1a</A>
Costa M.
Chiusoli GP.
Taffurelli D.
Dalmonego G.
J. Chem. Soc., Perkin Trans. 1
1998,
1541
<A NAME="RE14305SS-1B">1b</A>
Kovacevic B.
Maksic ZB.
Org. Lett.
2001,
3:
1523
<A NAME="RE14305SS-2">2</A>
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
<A NAME="RE14305SS-3A">3a</A>
Isobe T.
Fukuda K.
Ishikawa T.
J. Org. Chem.
2000,
65:
7770
<A NAME="RE14305SS-3B">3b</A>
Isobe T.
Fukuda K.
Tokunaga T.
Seki H.
Yamaguchi K.
Ishikawa T.
J. Org. Chem.
2000,
65:
7774
<A NAME="RE14305SS-3C">3c</A>
Isobe T.
Fukuda K.
Yamaguchi K.
Seki H.
Tokunaga T.
Ishikawa T.
J. Org. Chem.
2000,
65:
7779
<A NAME="RE14305SS-4">4</A>
Ishikawa T.
Isobe T.
Chem. Eur. J.
2002,
8:
552
<A NAME="RE14305SS-5">5</A>
Schenck M.
Hoppe-Seyler’s Z. Physiol. Chem.
1912,
77:
370
<A NAME="RE14305SS-6">6</A>
Schenck M.
von Graevenitz F.
Hoppe-Seyler’s Z. Physiol. Chem.
1924,
141:
139-144
<A NAME="RE14305SS-7A">7a</A>
Tanaka K.
Kamatani M.
Mori H.
Fujii S.
Ikeda K.
Hisada M.
Itagaki Y.
Katsumura S.
Tetrahedron Lett.
1998,
39:
1185
<A NAME="RE14305SS-7B">7b</A>
Kocienski PJ.
Brown RCD.
Pommier A.
Procter M.
Schmidt B.
J. Chem. Soc., Perkin Trans. 1
1998,
9
<A NAME="RE14305SS-8A">8a</A>
Barton DHR.
Elliott JD.
Gero SD.
J. Chem. Soc., Chem. Commun.
1981,
1136
<A NAME="RE14305SS-8B">8b</A>
Barton DHR.
Elliott JD.
Gero SD.
J. Chem. Soc., Perkin Trans. 1
1982,
2085
<A NAME="RE14305SS-9A">9a</A>
Barton DHR.
Bashiardes G.
Fourrey J.-L.
Tetrahedron Lett.
1983,
24:
1605
<A NAME="RE14305SS-9B">9b</A>
Barton DHR.
Chen M.
Jaszberenyi JC.
Taylor DK.
Org. Synth.
1997,
74:
101
<A NAME="RE14305SS-10">10</A>
Furrow ME.
Myers AG.
J. Am. Chem. Soc.
2004,
126:
5436
<A NAME="RE14305SS-11A">11a</A>
Wipf P.
Lynch SM.
Org. Lett.
2003,
5:
1155
<A NAME="RE14305SS-11B">11b</A>
Wipf P.
Lynch SM.
Birmingham A.
Tamayo G.
Jimenez A.
Campos N.
Powis G.
Org. Biomol. Chem.
2004,
2:
1651
<A NAME="RE14305SS-12">12</A>
Cooper DM.
Grigg R.
Hargreaves S.
Kennewell P.
Redpath J.
Tetrahedron
1995,
51:
7791
<A NAME="RE14305SS-13A">13a</A>
Leadbeater NE.
van der Pol C.
J. Chem. Soc., Perkin Trans. 1
2001,
2831
<A NAME="RE14305SS-13B">13b</A>
Graunger RS.
Leadbeater NE.
Pamies MA.
Catal. Commun.
2002,
3:
449
<A NAME="RE14305SS-14A">14a</A>
Fedorov A.
Combes S.
Finet J.-P.
Tetrahedron
1999,
55:
1341
<A NAME="RE14305SS-14B">14b</A>
Matano Y.
Imahori H.
J. Org. Chem.
2004,
69:
5505
<A NAME="RE14305SS-15">15</A>
Anastasia M.
Allevi P.
Ciuffeda P.
Fiecchi A.
Synthesis
1983,
123
<A NAME="RE14305SS-16A">16a</A>
Travins JM.
Etzkorn FA.
J. Org. Chem.
1997,
62:
8387
<A NAME="RE14305SS-16B">16b</A>
Debenham SD.
Debenham JS.
Burk MJ.
Toone EJ.
J. Am. Chem. Soc.
1997,
119:
9897
<A NAME="RE14305SS-16C">16c</A>
Varie DL.
Brennam J.
Briggs B.
Cronin JS.
Hay DA.
Rieck JA.
Zmijewski MJ.
Tetrahedron Lett.
1998,
39:
8405
<A NAME="RE14305SS-16D">16d</A>
Ritzen A.
Basu B.
Waellgerg A.
Frejd T.
Tetrahedron: Asymmetry
1998,
9:
3491
<A NAME="RE14305SS-17A">17a</A>
Huang J.
Jiang T.
Gao H.
Han B.
Liu Z.
Wu W.
Chang Y.
Zhao G.
Angew. Chem. Int. Ed.
2004,
43:
1397
<A NAME="RE14305SS-17B">17b</A>
Yang Y.
Deng C.
Yuan Y.
J. Catal.
2005,
232:
108
<A NAME="RE14305SS-17C">17c</A>
Zhu A.
Jiang T.
Wang D.
Han B.
Liu L.
Huang J.
Zhang J.
Sun D.
Green Chem.
2005,
7:
514
<A NAME="RE14305SS-17D">17d</A>
Wang P.
Zakeeruddin SM.
Graetzel M.
Kantlehner W.
Mezger J.
Stoyanov EV.
Scherr O.
App. Phys. A: Mater. Sci. Process.
2004,
79:
73
<A NAME="RE14305SS-18">18</A>
Nysted LN.
Burtner RR.
J. Org. Chem.
1962,
27:
3175
<A NAME="RE14305SS-19A">19a</A>
Pollini GP.
Barco A.
De Giuli G.
Synthesis
1972,
44
<A NAME="RE14305SS-19B">19b</A>
Alvarez FS.
Wren D.
Tetrahedron Lett.
1973,
569
<A NAME="RE14305SS-19C">19c</A>
Hewson AT.
MacPherson DT.
Tetrahedron Lett.
1983,
24:
647
<A NAME="RE14305SS-19D">19d</A>
Naito T.
Honda Y.
Bhavakul V.
Yamaguchi S.
Fujiwara A.
Miyata O.
Ninomiya I.
Chem. Pharm. Bull.
1997,
45:
1932
<A NAME="RE14305SS-20">20</A>
Nagasawa K.
Georgieva A.
Takahashi H.
Nakata T.
Tetrahedron
2001,
57:
8959
<A NAME="RE14305SS-21">21</A>
Simoni D.
Invidiata FP.
Manferdini M.
Lampronti I.
Rondonin R.
Roberti M.
Pollini GP.
Tetrahedron Lett.
1998,
39:
7615
<A NAME="RE14305SS-22A">22a</A>
Forsyth AC.
Paton RM.
Watt I.
Tetrahedron Lett.
1989,
30:
993
<A NAME="RE14305SS-22B">22b</A>
Hossain N.
Garg N.
Chattopadhyaya J.
Tetrahedron
1993,
49:
10061
<A NAME="RE14305SS-23A">23a</A>
Xia Y.
Kozikowski AP.
J. Am. Chem. Soc.
1989,
111:
4116
<A NAME="RE14305SS-23B">23b</A>
Kozikowski AP.
Prakash KRC.
Saxena A.
Doctor BP.
Chem. Commun.
1998,
1287
<A NAME="RE14305SS-24">24</A>
Simoni D.
Invidiata FP.
Manfredini S.
Ferroni R.
Lampronti I.
Roberti M.
Pollini GP.
Tetrahedron Lett.
1997,
38:
2749
<A NAME="RE14305SS-25A">25a</A>
Hossain N.
Herdewijn P.
Nucleosides Nucleotides
1998,
17:
1781
<A NAME="RE14305SS-25B">25b</A>
Hossain N.
van Halbeek H.
De Clercq E.
Herdewijn P.
Tetrahedron
1998,
54:
2209
<A NAME="RE14305SS-25C">25c</A>
Ishikawa T.
Shimizu Y.
Kudoh T.
Saito S.
Org. Lett.
2003,
5:
3879
<A NAME="RE14305SS-26">26</A>
Bernardi L.
Bonini BF.
Capito E.
Dessole G.
Comes-Franchini M.
Fochi M.
Ricci A.
J. Org. Chem.
2004,
69:
8168
<A NAME="RE14305SS-27A">27a</A>
Van Aken E.
Wynberg H.
Van Bolhuis F.
J. Chem. Soc., Chem. Commun.
1992,
629
<A NAME="RE14305SS-27B">27b</A>
Van Aken E.
Wynberg H.
Van Bolhuis F.
Acta Chem. Scand.
1993,
47:
122
<A NAME="RE14305SS-28">28</A>
Bera S.
Langley GJ.
Pathak T.
J. Org. Chem.
1998,
63:
1754
<A NAME="RE14305SS-29">29</A>
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
<A NAME="RE14305SS-30">30</A>
Luzzio FA.
Mayorov AV.
Synlett
2003,
532
<A NAME="RE14305SS-31">31</A>
Li S.
Xie H.
Zhang S.
Lin Y.
Xu J.
Cao J.
Synlett
2005,
1885
<A NAME="RE14305SS-32">32</A>
Kim S.
Chang H.
Synth. Commun.
1984,
14:
899
<A NAME="RE14305SS-33">33</A>
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
<A NAME="RE14305SS-34A">34a</A>
Sercheli R.
Vargas RM.
Sheldon RA.
Schuchardt U.
J. Mol. Catal. A: Chem.
1999,
148:
173
<A NAME="RE14305SS-34B">34b</A>
Blanc AC.
Valle S.
Renard G.
Brunel D.
Macquarrie DJ.
Quinn CR.
Green Chem.
2000,
2:
283
<A NAME="RE14305SS-34C">34c</A>
Simoni D.
Rondanin R.
Morini M.
Baruchello R.
Invidiata GP.
Tetrahedron Lett.
2000,
41:
1607
<A NAME="RE14305SS-34D">34d</A>
Macquarrie DJ.
Utting KA.
Brunel D.
Renard G.
Blanc A.
Stud. Surf. Sci. Catal.
2002,
142B:
1473
<A NAME="RE14305SS-34E">34e</A>
Kim K.-S.
Song JH.
Kim J.-H.
Seo G.
Stud. Surf. Sci. Catal.
2003,
146:
505
<A NAME="RE14305SS-34F">34f</A>
Jerome F.
Kharchafi G.
Adam I.
Barrault J.
Green Chem.
2004,
6:
72
<A NAME="RE14305SS-35">35</A>
Papa AJ.
J. Org. Chem.
1966,
31:
1426
<A NAME="RE14305SS-36">36</A>
Xiao D.
Carroll PJ.
Mayer SC.
Pfizenmayer AJ.
Joullie MM.
Tetrahedron: Asymmetry
1997,
8:
3043
<A NAME="RE14305SS-37A">37a</A>
Evans DA.
Ellman JA.
Dorow RL.
Tetrahedron Lett.
1987,
28:
1123
<A NAME="RE14305SS-37B">37b</A>
Evans DA.
Britton TC.
Ellman JA.
Dorow RL.
J. Am. Chem. Soc.
1990,
112:
4011
<A NAME="RE14305SS-37C">37c</A>
Stone MJ.
Maplestone RA.
Rahman SK.
Williams DH.
Tetrahedron Lett.
1991,
32:
2663
<A NAME="RE14305SS-37D">37d</A>
Boteju LW.
Wegner K.
Hruby V.
Tetrahedron Lett.
1992,
33:
7491
<A NAME="RE14305SS-37E">37e</A>
Dharanipragada R.
VanHulle K.
Bannister A.
Bear S.
Kennedy L.
Hruby VJ.
Tetrahedron
1992,
48:
4733
<A NAME="RE14305SS-37F">37f</A>
Davis AP.
Orchard MG.
J. Chem. Soc., Perkin Trans. 1
1993,
919
<A NAME="RE14305SS-37G">37g</A>
Larsson U.
Carison R.
Leroy J.
Acta Chem. Scand.
1993,
47:
380
<A NAME="RE14305SS-37H">37h</A>
Li C.
Arasappan A.
Fuchs PL.
Tetrahedron Lett.
1993,
34:
3535
<A NAME="RE14305SS-37I">37i</A>
Li C.
Shih T.-L.
Jeong JU.
Arasappan A.
Fuchs PL.
Tetrahedron Lett.
1994,
35:
2645
<A NAME="RE14305SS-37J">37j</A>
Palacios F.
Aparicio D.
de los Santos JM.
Perez de Heredia I.
Rubiales G.
Org. Prep. Proced. Int.
1995,
27:
171
<A NAME="RE14305SS-37K">37k</A>
Crotti P.
Di Bussolo V.
Favero L.
Macchia F.
Pineschi M.
Tetrahedron Lett.
1996,
37:
1675
<A NAME="RE14305SS-37L">37l</A>
Radel PA.
Kahl SB.
J. Org. Chem.
1996,
61:
4582
<A NAME="RE14305SS-37M">37m</A>
Liao S.
Shenderovich MD.
Lin J.
Hruby VJ.
Tetrahedron
1997,
53:
16645
<A NAME="RE14305SS-37N">37n</A>
Bhattarai KM.
Davis AP.
Perry JJ.
Walter CJ.
Menzer S.
Williams DJ.
J. Org. Chem.
1997,
62:
8463
<A NAME="RE14305SS-37O">37o</A>
LeMerrer Y.
Gravier-Pelletier C.
Gerrouache M.
Depezay J.-C.
Tetrahedron Lett.
1998,
39:
385
<A NAME="RE14305SS-37P">37p</A>
Kinugasa M.
Harada T.
Oku A.
Tetrahedron Lett.
1998,
39:
4529
<A NAME="RE14305SS-37Q">37q</A>
Gibson CL.
Gillon K.
Cook S.
Tetrahedron Lett.
1998,
39:
6733
<A NAME="RE14305SS-37R">37r</A>
Hentemann M.
Fuchs PL.
Tetrahedron Lett.
1999,
40:
2699
<A NAME="RE14305SS-37S">37s</A>
Ballereau S.
McCort I.
Dureault A.
Depezay J.-C.
Tetrahedron
2001,
57:
1935
<A NAME="RE14305SS-37T">37t</A>
Denmark SE.
Dorow RL.
Chirality
2002,
14:
241
<A NAME="RE14305SS-37U">37u</A>
Smith RJ.
Bienz S.
Helv. Chim. Acta
2004,
87:
1681
<A NAME="RE14305SS-37V">37v</A>
Di Bussolo V.
Caselli M.
Romano MR.
Pineschi M.
Crotti P.
J. Org. Chem.
2004,
69:
8702
<A NAME="RE14305SS-37W">37w</A>
Treweeke NR.
Hitchcock PB.
Pardoe DA.
Caddick S.
Chem. Commun.
2005,
1868
<A NAME="RE14305SS-37X">37x</A>
Fotsing JR.
Hagedon M.
Banert K.
Tetrahedron
2005,
61:
8904
<A NAME="RE14305SS-38A">38a</A>
Chinchilla R.
Najera C.
Sanchez-Agullo P.
Tetrahedron: Asymmetry
1994,
5:
1393
<A NAME="RE14305SS-38B">38b</A>
Ma C.
Cheng K.
Tetrahedron: Asymmetry
1999,
10:
713
<A NAME="RE14305SS-39A">39a</A>
Davis AP.
Dempsey KJ.
Tetrahedron: Asymmetry
1995,
6:
2829
<A NAME="RE14305SS-39B">39b</A>
Corey EJ.
Grogan MJ.
Org. Lett.
1999,
1:
157
<A NAME="RE14305SS-40">40</A>
Iyer MS.
Gigstad KM.
Namdev ND.
Lipton M.
J. Am. Chem. Soc.
1996,
118:
4910
<A NAME="RE14305SS-41A">41a</A>
Howard-Jones A.
Murphy PJ.
Thomas DA.
Caulkett PWR.
J. Org. Chem.
1999,
64:
1039
<A NAME="RE14305SS-41B">41b</A>
Kita T.
Georgieva A.
Hashimoto Y.
Nakata T.
Nagasawa K.
Angew. Chem. Int. Ed.
2002,
41:
2832
<A NAME="RE14305SS-41C">41c</A>
Allingham MT.
Howard-Jones A.
Murphy PJ.
Thomas DA.
Caulkett PWR.
Tetrahedron Lett.
2003,
44:
8677
<A NAME="RE14305SS-42A">42a</A>
Isobe T.
Ishikawa T.
J. Org. Chem.
1999,
64:
5832
<A NAME="RE14305SS-42B">42b</A>
Isobe T.
Ishikawa T.
J. Org. Chem.
1999,
64:
6984
<A NAME="RE14305SS-42C">42c</A>
Isobe T.
Ishikawa T.
J. Org. Chem.
1999,
64:
6989
<A NAME="RE14305SS-42D">42d</A>
Merck Index
13th ed.:
Merck Publishing;
New Jersey:
2001.
p.596
<A NAME="RE14305SS-43">43</A>
Isobe T.
Fukuda K.
Ishikawa T.
Tetrahedron: Asymmetry
1998,
9:
1729
<A NAME="RE14305SS-44">44</A>
sobe, T.; Fukuda, K.; Ishikawa, T. unpublished results
<A NAME="RE14305SS-45">45</A>
Kitani Y.
Kumamoto T.
Isobe T.
Fukuda K.
Ishikawa T.
Adv. Synth. Catal.
2005,
347:
1653
<A NAME="RE14305SS-46A">46a</A>
Alcazar V.
Moran JR.
de Mendoza J.
Tetrahedron Lett.
1995,
36:
3941
<A NAME="RE14305SS-46B">46b</A>
Martin-Portugues M.
Alcazar V.
Prados P.
de Mendoza J.
Tetrahedron
2002,
58:
2951
<A NAME="RE14305SS-46C">46c</A> For the preparation of the related guanidines, see:
Echavarren A.
Galan A.
de Mendoza J.
Salmeron A.
Helv. Chim. Acta
1988,
71:
685
<A NAME="RE14305SS-46D">46d</A>
Gleich A.
Schmidtchen FP.
Chem. Ber.
1990,
123:
907
<A NAME="RE14305SS-47">47</A>
Ishikawa T.
Araki Y.
Kumamoto T.
Seki H.
Fukuda K.
Isobe T.
Chem. Commun.
2001,
245
For examples, see:
<A NAME="RE14305SS-48A">48a</A>
Metzger JO.
Angew. Chem. Int. Ed.
1998,
37:
2975
<A NAME="RE14305SS-48B">48b</A>
Tanaka K.
Toda F.
Chem. Rev.
2000,
100:
1025
<A NAME="RE14305SS-48C">48c</A>
Aggarwal VK.
Mereu A.
Chem. Commun.
2000,
2310
<A NAME="RE14305SS-49">49</A>
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
<A NAME="RE14305SS-50">50</A>
Pan Q.-B.
Ma D.-W.
Chin. J. Chem.
2003,
21:
793
<A NAME="RE14305SS-51">51</A>
Isobe T.
Fukuda K.
Araki Y.
Ishikawa T.
Chem. Commun.
2001,
243
<A NAME="RE14305SS-52">52</A>
Groeger H.
Chem. Rev.
2003,
103:
2795
<A NAME="RE14305SS-53">53</A>
Li J.
Jiang W.-Y.
Han K.-L.
He G.-Z.
Li C.
J. Org. Chem.
2003,
68:
8786
<A NAME="RE14305SS-54">54</A>
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
<A NAME="RE14305SS-55">55</A>
Wannaporn D.
Ishikawa T.
J. Org. Chem.
2005,
70:
9399
<A NAME="RE14305SS-56">56</A> With regard to the guanidinium ylide from N-fluorenyl-guanidinium iodide, see:
Lloyd D.
Millar RW.
J. Chem. Soc., Chem. Commun.
1976,
266
<A NAME="RE14305SS-57">57</A>
Haga T.
Ishikawa T.
Tetrahedron
2005,
61:
2857
<A NAME="RE14305SS-58">58</A>
Trost BM.
Yasukata T.
J. Am. Chem. Soc.
2001,
123:
7162
<A NAME="RE14305SS-59">59</A>
Hjelmencrantz A.
Berg U.
J. Org. Chem.
2002,
67:
3585
<A NAME="RE14305SS-60A">60a</A>
Koehn U.
Guenther W.
Goerls H.
Anders E.
Tetrahedron: Asymmetry
2004,
15:
1419
<A NAME="RE14305SS-60B">60b</A>
Koehn U.
Schulz M.
Goerls H.
Anders E.
Tetrahedron: Asymmetry
2005,
16:
2125
