Abstract
Structurally related to iodosylbenzene PhI=O, iodonium imidesPhI=NR, off-white to pale yellow solids of low solubility, belongto the class of hypervalent iodine(III) reagents and were first preparednearly thirty years ago. Two additional decades were needed beforethey could be considered as useful nitrene precursors with the discoveryof the copper-catalyzed aziridination of olefins. Since then, iminoiodaneshave been successfully applied in the total synthesis of naturaland/or biologically active compounds. Recent developmentsaimed at circumventing their tedious preparation led to the discoveryof one-pot nitrogen transfers from sulfonamides, sulfamates, orcarbamates mediated by iodosylbenzene(diacetate) PhI(OAc)2 oriodosylbenzene. Reliable functionalizations of alkanes and alkenesvia C-H insertion or aziridination using copper or rhodiumcatalysts can now be considered as synthetically useful processes.
-
1 Introduction
-
2 Iminoiodanes
-
2.1 General Properties
-
2.2 Methods of Preparation
-
2.3 Types of N-SubstitutedIminoiodanes
-
3 Iminoiodanes in Organic Synthesis
-
3.1 Natural Product Synthesis
-
3.2 Synthesis of Biologically Active Compounds
-
4 Recent Developments: Iodonium Ylides as in situ
Intermediates
-
4.1 Metalloporphyrin-Mediated Nitrogen Atom Transfer
-
4.2 Rhodium-Catalyzed Nitrogen Atom Transfer
-
4.3 Copper-Catalyzed Nitrogen Atom Transfer
-
5 Conclusion and Future Prospects
Key words
hypervalent iodine - iminoiodane - iodosylbenzene - iodosylbenzene diacetate - nitrene - aziridination - C-H insertion - copper catalyst - rhodiumcatalyst - total synthesis
References
For recent and representative reviewssee:
1a
Zdhankin VV.
Stang PJ.
Chem.Rev.
2002,
102:
2523
1b
Stang PJ.
Zdhankin VV.
Chem.Rev.
1996,
96:
1123
1c
Varvoglis A.
Tetrahedron
1997,
53:
1179
2
Willgerodt C.
Chem.Ber.
1892,
25:
3494
3
Yamada Y.
Yamamoto T.
Okawara M.
Chem.Lett.
1975,
361
4
Abramovitch RA.
Bailey TD.
Takaya T.
Uma V.
J. Org. Chem.
1974,
39:
340
5
Breslow R.
Gellman SH.
J. Chem. Soc., Chem.Commun.
1982,
1400
6a
Mansuy D.
Mahy J.-P.
Duréault A.
Bedi G.
Battioni P.
J. Chem. Soc., Chem. Commun.
1984,
1161
6b
Mahy J.-P.
Bedi G.
Battioni P.
Mansuy D.
J. Chem. Soc., Perkin Trans.2
1988,
1517
7a Preliminaryaccount: Evans DA.
Faul MM.
Bilodeau MT.
J.Org. Chem.
1991,
56:
6744
7b
Evans DA.
Faul MM.
Bilodeau MT.
J. Am. Chem. Soc.
1994,
116:
2742
8a
Evans DA.
Faul MM.
Bilodeau MT.
Anderson BA.
J. Am. Chem. Soc.
1993,
115:
5328
8b
Li Z.
Conser KR.
Jacobsen EN.
J. Am. Chem. Soc.
1993,
115:
5326
9a
Tanner D.
Angew. Chem., Int. Ed. Engl.
1994,
33:
599
9b
Osborn HMI.
Sweeney J.
Tetrahedron:Asymmetry
1997,
8:
1693
9c
McCoull W.
Davis FA.
Synthesis
2000,
1347
9d
Sweeney JB.
Chem. Soc. Rev.
2002,
31:
247
10a
Li Z.
Quan RW.
Jacobsen EN.
J. Am. Chem. Soc.
1995,
117:
5889
10b
Díaz-Requejo MM.
Pérez PJ.
Brookhart M.
Templeton JL.
Organometallics
1997,
16:
4399
10c
Brandt P.
Södergren MJ.
Andersson PG.
Norrby P.-O.
J.Am. Chem. Soc.
2000,
122:
8013
10d
Gillespie KM.
Crust EJ.
Deeth RJ.
Scott P.
Chem.Commun.
2001,
785
11
Katsuki T.
AsymmetricEpoxidation of Unfunctionalized Olefins and Related Reactions In Catalytic Asymmetric Synthesis
Ojima I.
Wiley-VCH;
NewYork:
2000.
p.317-325
12 For a general overview on nitrenetransfer see: Müller P.
TransitionMetal-Catalyzed Nitrene Transfer In Advancesin Catalytic Processes
Vol. 2:
Doyle MP.
JAI Press Inc.;
GreenwichCT:
1997.
p.113-151
13a Pioneeringobservation: Breslow R.
Gellman SH.
J. Am. Chem. Soc.
1983,
105:
6728
13b
Müller P.
Baud C.
Jacquier Y.
Moran M.
Nägeli I.
J. Phys. Org. Chem.
1996,
9:
341
13c For a recent enantioselectiveRh(II)-catalyzed C-H insertion: Yamawaki M.
Tsutsui H.
Kitagaki S.
Anada M.
Hashimoto S.
TetrahedronLett.
2002,
43:
9561
14
Espino CG.
Du Bois J.
Angew. Chem. Int. Ed.
2001,
40:
598
15
Boucher M.
Macikenas D.
Ren T.
Protasiewicz JD.
J. Am. Chem.Soc.
1997,
119:
9366
16
White RE.
Inorg.Chem.
1987,
26:
3916
17
Macikenas D.
Meprathu BV.
Protasiewicz JD.
Tetrahedron Lett.
1998,
39:
191
18
Besenyei G.
Németh S.
Simándi LI.
Tetrahedron Lett.
1993,
34:
6105
19
Dauban P.
Dodd RH.
J. Org. Chem.
1999,
64:
5304
20
Södergren MJ.
Alonso DA.
Bedekar AV.
Andersson PG.
TetrahedronLett.
1997,
38:
6897
21
Meprathu BV.
Diltz S.
Walsh PJ.
Protasiewicz JD.
TetrahedronLett.
1999,
40:
5459
22
Macikenas D.
Skrzypczak-Jankun E.
Protasiewicz JD.
J. Am. Chem. Soc.
1999,
121:
7164
23
Alonso DA.
Andersson PG.
J. Org. Chem.
1998,
65:
9455
24
Bergmeier SC.
Seth PP.
Tetrahedron Lett.
1999,
40:
6181
25
Södergren MJ.
Alonso DA.
Andersson PG.
Tetrahedron: Asymmetry
1997,
8:
3563
26
Maligres PE.
See MM.
Askin D.
Reider PJ.
Tetrahedron Lett.
1997,
38:
5253
27
Fukuyama T.
Cheung M.
Jow C.-K.
Hidai Y.
Kan T.
TetrahedronLett.
1995,
39:
3889
28 Dauban, P.; Dodd, R.H. unpublished results.
29
Dauban P.
Dodd RH.
Org. Lett.
2000,
2:
2327
30
Moriarty RM.
Chany CJ.
Vaid RK.
Prakash O.
Tuladhar SM.
J. Org. Chem.
1993,
58:
2478
31a
Hudlicky T.
Tian X.
Königsberger K.
Rouden J.
J. Org.Chem.
1994,
59:
4037
31b
Hudlicky T.
Tian X.
Königsberger K.
Maurya R.
Rouden J.
Fan B.
J. Am. Chem. Soc.
1996,
118:
10752
32
Knight JG.
Muldowney MP.
Synlett
1995,
949
33
Baron E.
O’Brien P.
Towers TD.
Tetrahedron Lett.
2002,
43:
723
34
Caine D.
O’Brien P.
Rosser CM.
Org. Lett.
2002,
4:
1923
35
White RD.
Wood JL.
Org. Lett.
2001,
3:
1825
36
Sudau A.
Münch W.
Bats JW.
Nubbemeyer U.
Chem.-Eur. J.
2001,
7:
611
For a recent improvement see:
37a
Sanders CJ.
Gillespie KM.
Bell D.
Scott P.
J. Am. Chem.Soc.
2000,
122:
7132
37b
Gillespie KM.
Sanders CJ.
O’Shaughnessy P.
Westmoreland I.
Thickitt CP.
Scott P.
J.Org. Chem.
2002,
67:
3450
38
Overman LE.
Tomasi AL.
J. Am. Chem. Soc.
1998,
120:
4039
39 For an asymmetric version of thecopper-catalyzed aziridination of enol derivatives see: Adam W.
Roschmann KJ.
Saha-Möller CR.
Eur. J. Org. Chem.
2000,
557
40
Li L.-S.
Wu Y.-L.
Wu Y.
Org.Lett.
2000,
2:
891
41
Flock S.
Frauenrath H.
Synlett
2001,
839
42
Molander GA.
Stengel PJ.
Tetrahedron
1997,
53:
8887
43
Pak CS.
Kim TH.
Ha SJ.
J.Org. Chem.
1998,
63:
10006
44
Kim DY.
Rhie DY.
Tetrahedron
1997,
53:
13603
45
Dauban P.
Dodd RH.
Tetrahedron Lett.
1998,
39:
5739
46a
Paul BJ.
Martinot TA.
Willis J.
Hudlicky T.
Synthesis
2001,
952
46b
Paul BJ.
Willis J.
Martinot TA.
Ghiviriga I.
Abboud KA.
Hudlicky T.
J.Am. Chem. Soc.
2002,
124:
10416
47
Ahmadian M.
Khare NK.
Riordan JM.
Klon AE.
Borhani DW.
Tetrahedron
2001,
57:
9899
48
Regueiro-Ren A.
Borzilleri RM.
Zheng X.
Kim S.-H.
Johnson JA.
Fairchild CR.
Lee FYF.
Long BH.
Vite GD.
Org. Lett.
2001,
3:
2693
49
Masse CE.
Knight BS.
Stavropoulos P.
Panek JS.
J. Am. Chem. Soc.
1997,
119:
6040
50
Yang J.
Weinberg R.
Breslow R.
Chem.Commun.
2000,
531
51
Di Chenna PH.
Dauban P.
Ghini A.
Burton G.
Dodd RH.
TetrahedronLett.
2000,
41:
7041
52
Dauban P.
Ferry S.
Faure H.
Ruat M.
Dodd RH.
Bioorg.Med. Chem. Lett.
2000,
10:
2001
53 Kessler, A.; Faure, H.; Ruat, M.;Dauban, P.; Dodd, R. H. to be published.
54 Kessler, A.; Faure, H.; Ruat, M.;Dauban, P.; Dodd, R. H. to be published.
55a
Yu X.-Q.
Huang J.-S.
Zhou X.-G.
Che C.-M.
Org. Lett.
2000,
2:
2233
55b
Au S.-M.
Huang J.-S.
Che C.-M.
Yu W.-Y.
J. Org. Chem.
2000,
65:
7858
55c
Liang J.-L.
Huang J.-S.
Yu X.-Q.
Zhu N.
Che C.-M.
Chem.-Eur.J.
2002,
7:
1563
56
Liang J.-L.
Yuan S.-X.
Huang J.-S.
Yu W.-Y.
Che C.-M.
Angew.Chem. Int. Ed.
2002,
41:
3465
57
Espino CG.
Wehn PM.
Chow J.
Du Bois J.
J. Am. Chem. Soc.
2001,
123:
6935
58
Wehn PM.
Du Bois J.
J. Am. Chem. Soc.
2002,
124:
12950
59
Levites-Agababa E.
Menhaji E.
Perlson LN.
Rojas CM.
Org. Lett.
2002,
4:
863
60
Padwa A.
Stengel T.
Org. Lett.
2002,
4:
2137
61
Guthikonda K.
Du Bois J.
J. Am. Chem. Soc.
2002,
124:
13672
62 During the preparation of this accounta paper from Che appeared describing the one-pot intramolecularrhodium-catalyzed aziridination starting from unsaturated sulfonamidesand mediated by PhI(OAc)2 and Al2O3: Liang J.-L.
Yuan S.-X.
Hong Chan PW.
Che C.-M.
Org.Lett.
2002,
4:
4507
63
Schardt BC.
Hill CL.
Inorg. Chem.
1983,
22:
1563
64
Dauban P.
Sanière L.
Tarrade A.
Dodd RH.
J. Am. Chem. Soc.
2001,
123:
7707
For some representative examples:
65a
Lichtenberger F.
Nastainczyk W.
Ullrich V.
Biochem. Biophys. Res. Commun.
1976,
71:
939
65b
Groves JT.
Nemo TE.
J. Am.Chem. Soc.
1983,
105:
5786
65c
Franklin CC.
VanAtta RB.
FanTai A.
Valentine JS.
J.Am. Chem. Soc.
1984,
106:
814
65d
Zhang W.
Loebach JL.
Wilson SR.
Jacobsen EN.
J.Am. Chem. Soc.
1990,
112:
2801
65e
Nam W.
Valentine JS.
J. Am. Chem. Soc.
1990,
112:
4977
65f
Yang Y.
Diederich F.
Valentine JS.
J.Am. Chem. Soc.
1991,
113:
7195
65g
Nam W.
Valentine JS.
J. Am. Chem. Soc.
1991,
113:
7449
65h
Collman JP.
Zhang X.
Lee VJ.
Uffelman ES.
Brauman JI.
Science
1993,
261:
1404
66
Duran F.
Leman L.
Ghini A.
Burton G.
Dauban P.
Dodd RH.
Org. Lett.
2002,
4:
2481
67 Sanière, L.; Leman, L.; Bourguignon,J.-J.; Dauban, P.; Dodd, R. H. to be published.
For recents methods of aziridinationof olefins see:
68a
Jeong JU.
Tao B.
Sagasser I.
Henniges H.
Sharpless KB.
J.Am. Chem. Soc.
1998,
120:
6844
68b
Iliyas Ali S.
Nikalje MD.
Sudalai A.
Org.Lett.
1999,
1:
705
68c
Chanda BM.
Vyas R.
Bedekar AV.
J. Org. Chem.
2001,
66:
30
68d
Atkinson RS.
Tetrahedron
1999,
55:
1519
68e
Nishimura M.
Minakata S.
Takahashi T.
Oderaotoshi Y.
Komatsu M.
J.Org. Chem.
2002,
67:
2101
68f
Siu T.
Yudin AK.
J. Am. Chem. Soc.
2002,
124:
530
69 For a recent review: Togo H.
Sakuratani K.
Synlett
2002,
1966
