Subscribe to RSS
DOI: 10.1055/s-2005-862381
Cp*Ir Complex-Catalyzed Hydrogen Transfer Reactions Directed toward Environmentally Benign Organic Synthesis
Publication History
Publication Date:
22 February 2005 (online)
![](https://www.thieme-connect.de/media/synlett/200504/lookinside/thumbnails/10.1055-s-2005-862381-1.jpg)
Abstract
Catalytic activity of Cp*Ir complexes toward hydrogen transfer reactions are discussed. Three different types of reactions have been developed. The first is Oppenauer-type oxidation of alcohols. This reaction proceeds under quite mild conditions (room temperature in acetone) catalyzed by [Cp*IrCl2]2/K2CO3, and both primary and secondary alcohols can be used as substrates. Introduction of a N-heterocyclic carbene ligand to the catalyst considerably enhances the catalytic activity, and a very high turnover number of 950 has been obtained in the oxidation of 1-phenylethanol. The second is the N-alkylation of amines with alcohols. A new effective catalytic system consisting of [Cp*IrCl2]2/K2CO3 for the N-alkylation of primary amines with alcohols has been developed. Synthesis of indoles and 1,2,3,4-tetrahydroquinolines via intramolecular N-alkylation of amino alcohols and synthesis of nitrogen heterocycles via intermolecular N-alkylation of primary amines with diols catalyzed by a Cp*Ir complex have been also achieved. The third is the regio- and chemoselective transfer hydrogenation of quinolines. An efficient method for the transfer hydrogenation of quinolines catalyzed by [Cp*IrCl2]2/HClO4 using 2-propanol as a hydrogen source has been realized. A variety of 1,2,3,4-tetrahydroquinoline derivatives can be synthesized by this method. These results show that Cp*Ir complexes can be useful catalysts for hydrogen transfer reactions from the viewpoint of developing environmentally benign organic synthesis.
-
1 Introduction
-
2 Hydrogen Transfer Oxidation of Primary and Secondary Alcohols (Oppenauer-Type Oxidation)
-
3 N-Alkylation of Amines with Alcohols
-
4 Synthesis of N-Heterocyclic Compounds
-
4.1 Intramolecular N-Heterocyclization of Amino Alcohols
-
4.2 Intermolecular N-Heterocyclization of Primary Amines with Diols
-
5 Transfer Hydrogenation of Quinolines
-
6 Conclusion
Key words
iridium - catalysis - hydrogen transfer - alcohols - amines
-
1a
Weissermel K.Arpe H.-J. Industrial Organic Chemistry 3rd ed.: VCH; New York: 1997. -
1b
Tsuji J. Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis Wiley; Chichester: 2000. -
1c
Comprehensive Organometallic Chemistry II
Vol. 12:
Abel EW.Stone FGA.Wilkinson G. Pergamon; Oxford: 1995. -
2a
Vaska L.DiLuzio JW. J. Am. Chem. Soc. 1961, 83: 2784 -
2b
Vaska L.DiLuzio JW. J. Am. Chem. Soc. 1962, 84: 679 -
2c
Vaska L. Acc. Chem. Res. 1968, 1: 335 -
3a
Crabtree RH.Morris GE. J. Organomet. Chem. 1977, 135: 395 -
3b
Crabtree RH.Felkin H.Morris GE. J. Organomet. Chem. 1977, 141: 205 -
3c
Crabtree RH. Acc. Chem. Res. 1979, 12: 331 -
3d
Crabtree RH.Davis MW. J. Org. Chem. 1986, 51: 2655 -
4a
Stork G.Kahne DE. J. Am. Chem. Soc. 1983, 105: 1072 -
4b
Lightfoot A.Schnider P.Pfaltz A. Angew. Chem. Int. Ed. 1998, 37: 2897 -
4c
Pfaltz A.Blankenstein J.Hilgraf R.Hörmann E.McIntyre S.Menges F.Schönleber M.Smidt SP.Wüstenberg B.Zimmermann N. Adv. Synth. Catal. 2003, 345: 33 -
4d
Tang W.Wang W.Zhang X. Angew. Chem. Int. Ed. 2003, 42: 943 -
4e
Jiang X.Minnaard AJ.Hessen B.Feringa BL.Duchateau ALL.Andrien JGO.Boogers JAF.de Vries JG. Org. Lett. 2003, 5: 1503 -
5a
Tanke RS.Crabtree RH. J. Am. Chem. Soc. 1990, 112: 7984 -
5b
Chatani N.Ikeda S.Ohe K.Murai S. J. Am. Chem. Soc. 1992, 114: 9710 -
5c
Jun C.-H.Crabtree RH. J. Organomet. Chem. 1993, 447: 177 -
5d
Nishibayashi Y.Segawa K.Singh JD.Fukuzawa S.Ohe K.Uemura S. Organometallics 1996, 15: 370 -
6a
Takeuchi R.Kashio M. Angew. Chem., Int. Ed. Engl. 1997, 36: 263 -
6b
Janssen JP.Helmchen G. Tetrahedron Lett. 1997, 38: 8025 -
6c
Takeuchi R.Kashio M. J. Am. Chem. Soc. 1998, 120: 8647 -
6d
Fuji K.Kinoshita N.Tanaka K.Kawabata T. Chem. Commun. 1999, 2289 -
6e
Takeuchi R. Polyhedron 2000, 19: 557 -
6f
Kanayama T.Yoshida K.Miyabe H.Takemoto Y. Angew. Chem. Int. Ed. 2003, 42: 2054 -
6g
Lipowsky G.Miller N.Helmchen G. Angew. Chem. Int. Ed. 2004, 43: 4595 -
7a
Jun C.-H.Lu Z.Crabtree RH. Tetrahedron Lett. 1992, 33: 7119 -
7b
Murakami M.Itami K.Ubukata M.Tsuji I.Ito Y. J. Org. Chem. 1998, 63: 4 -
7c
Takaya H.Naota T.Murahashi S.-I. J. Am. Chem. Soc. 1998, 120: 4244 -
7d
Ohmura T.Yorozuya S.Yamamoto Y.Miyaura N. Organometallics 2000, 19: 365 -
7e
Matsuda I.Makino T.Hasegawa Y.Itoh K. Tetrahedron Lett. 2000, 41: 1409 -
7f
Higashino T.Sakaguchi S.Ishii Y. Org. Lett. 2000, 2: 4193 -
7g
Chatani N.Inoue H.Morimoto T.Muto T.Murai S. J. Org. Chem. 2001, 66: 4433 -
7h
Takeuchi R.Tanaka S.Nakaya Y. Tetrahedron Lett. 2001, 42: 2991 -
7i
Shibata T.Yamashita K.Ishida H.Takagi K. Org. Lett. 2001, 3: 1217 -
7j
Sakaguchi S.Kubo T.Ishii Y. Angew. Chem. Int. Ed. 2001, 40: 2534 -
7k
Fischer C.Carreira EM. Org. Lett. 2001, 3: 4319 -
7l
Yasukawa T.Satoh T.Miura M.Nomura M. J. Am. Chem. Soc. 2002, 124: 12680 -
7m
Koike T.Du X.Sanada T.Danda Y.Mori A. Angew. Chem. Int. Ed. 2003, 42: 89 -
7n
Nakagawa H.Sakaguchi S.Ishii Y. Chem. Commun. 2003, 502 -
7o
Dorta R.Togni A. Chem. Commun. 2003, 760 -
7p
Yamazaki Y.Fujita K.Yamaguchi R. Chem. Lett. 2004, 33: 1316 -
8a
Takeuchi R.Shiga N. Org. Lett. 1999, 1: 265 -
8b
Takeuchi R.Ue N.Tanabe K.Yamashita K.Shiga N. J. Am. Chem. Soc. 2001, 123: 9525 -
8c
Ohmura T.Hartwig JF. J. Am. Chem. Soc. 2002, 124: 15164 -
8d
López F.Ohmura T.Hartwig JF. J. Am. Chem. Soc. 2003, 125: 3426 -
8e
Shu C.Hartwig JF. Angew. Chem. Int. Ed. 2004, 43: 4794 -
8f
Shu C.Leitner A.Hartwig JF. Angew. Chem. Int. Ed. 2004, 43: 4797 -
9a
Casalnuovo AL.Calabrese JC.Milstein D. J. Am. Chem. Soc. 1988, 110: 6738 -
9b
Kubo T.Sakaguchi S.Ishii Y. Chem. Commun. 2000, 625 -
9c
Nakagawa H.Okimoto Y.Sakaguchi S.Ishii Y. Tetrahedron Lett. 2003, 44: 103 -
10a
Inoue S.Nomura K.Hashiguchi S.Noyori R.Izawa Y. Chem. Lett. 1997, 957 -
10b
Tani K.Iseki A.Yamagata T. Chem. Commun. 1999, 1821 -
10c
Ajjou AN. Tetrahedron Lett. 2001, 42: 13 -
10d
Sakaguchi S.Yamaga T.Ishii Y. J. Org. Chem. 2001, 66: 4710 -
10e
Hillier AC.Lee HM.Stevens ED.Nolan SP. Organometallics 2001, 20: 4246 -
10f
Albrecht M.Miecznikowski JR.Samuel A.Faller JW.Crabtree RH. Organometallics 2002, 21: 3596 -
10g
Edwards MG.Williams JMJ. Angew. Chem. Int. Ed. 2002, 41: 4740 -
10h
Taguchi K.Nakagawa H.Hirabayashi T.Sakaguchi S.Ishii Y. J. Am. Chem. Soc. 2004, 126: 72 -
10i
Cami-Kobeci G.Williams JMJ. Chem. Commun. 2004, 1072 -
11a
Iverson CN.Smith MR. J. Am. Chem. Soc. 1999, 121: 7696 -
11b
Cho J.-Y.Tse MK.Holmes D.Maleczka RE.Smith MR. Science 2002, 295: 305 -
11c
Ishiyama T.Takagi J.Ishida K.Miyaura N.Anastasi NR.Hartwig JF. J. Am. Chem. Soc. 2002, 124: 390 -
11d
Ishiyama T.Takagi J.Hartwig JF.Miyaura N. Angew. Chem. Int. Ed. 2002, 41: 3056 -
11e
Maleczka RE.Shi F.Holmes D.Smith MR. J. Am. Chem. Soc. 2003, 125: 7792 -
11f
Mertins K.Zapf A.Beller M. J. Mol. Catal. A: Chem. 2004, 207: 21 -
11g
Ishiyama T.Miyaura N. Chem. Rec. 2004, 3: 271 -
12a
Gupta M.Kaska WC.Jensen CM. Chem. Commun. 1997, 461 -
12b
Jensen CM. Chem. Commun. 1999, 2443 -
12c
Liu F.Pak EB.Singh B.Jensen CM.Goldman AS. J. Am. Chem. Soc. 1999, 121: 4086 -
12d
Renkema KB.Kissin YV.Goldman AS. J. Am. Chem. Soc. 2003, 125: 7770 -
13a
Matsumoto T.Taube DJ.Periana RA.Taube H.Yoshida H. J. Am. Chem. Soc. 2000, 122: 7414 -
13b
Nishinaka Y.Satoh T.Miura M.Morisaka H.Nomura M.Matsui H.Yamaguchi C. Bull. Chem. Soc. Jpn. 2001, 74: 1727 -
13c
Hickey MJ.Jones JR.Kingston LP.Lockley WJS.Mather AN.McAuley BM.Wilkinson DJ. Tetrahedron Lett. 2003, 44: 3959 -
14a
Kang JW.Moseley K.Maitlis PM. J. Am. Chem. Soc. 1969, 91: 5970 -
14b
Maitlis PM. Acc. Chem. Res. 1978, 11: 301 -
14c See also:
Booth BL.Haszeldine RN.Hill M. J. Organomet. Chem. 1969, 16: 491 -
15a
Ball RG.Graham WAG.Heinekey DM.Hoyano JK.McMaster AD.Mattson BM.Michel ST. Inorg. Chem. 1990, 29: 2023 -
15b
White C.Yates A.Maitlis PM. Inorg. Synth. 1992, 29: 228 -
16a
Janowicz AH.Bergman RG. J. Am. Chem. Soc. 1982, 104: 352 -
16b
Janowicz AH.Bergman RG. J. Am. Chem. Soc. 1983, 105: 3929 -
16c
Arndtsen BA.Bergman RG. Science 1995, 270: 1970 -
16d
Tellers DM.Yung CM.Arndtsen BA.Adamson DR.Bergman RG. J. Am. Chem. Soc. 2002, 124: 1400 -
17a
Hoyano JK.Graham WAG. J. Am. Chem. Soc. 1982, 104: 3723 -
17b
Chetcuti PA.Knobler CB.Hawthorne MF. Organometallics 1988, 7: 650 -
17c
Fujita K.Nakaguma H.Hamada T.Yamaguchi R. J. Am. Chem. Soc. 2003, 125: 12368 -
17d See also:
Haddleton DM.Perutz RN. J. Chem. Soc., Chem. Commun. 1986, 1734 -
17e
Bell TW.Haddleton DM.McCamley A.Partridge MG.Perutz RN.Willner H. J. Am. Chem. Soc. 1990, 112: 9212 -
18a
Carmona D.Lahoz FJ.Elipe S.Oro LA.Lamata MP.Viguri F.Mir C.Cativiela C.López-Ram de Víu MP. Organometallics 1998, 17: 2986 -
18b
Mashima K.Abe T.Tani K. Chem. Lett. 1998, 1199 -
18c
Adams RD.Barnard TS.Brosius K. J. Organomet. Chem. 1999, 582: 358 -
18d
Murata K.Ikariya T.Noyori R. J. Org. Chem. 1999, 64: 2186 -
18e
Ogo S.Makihara N.Watanabe Y. Organometallics 1999, 18: 5470 -
19a
Leigh GJ.Richards RL. In Comprehensive Organometallic Chemistry Vol. 5:Abel EW.Stone FGA.Wilkinson G. Pergamon; Oxford: 1982. p.541-628 -
19b
Atwood JD. In Comprehensive Organometallic Chemistry II Vol. 8:Abel EW.Stone FGA.Wilkinson G. Pergamon; Oxford: 1995. p.303-417 -
19c
Merola JS. Curr. Org. Chem. 1997, 1: 235 -
19d
Takeuchi R. Synlett 2002, 1954 -
19e
Ishii Y.Sakaguchi S. Bull. Chem. Soc. Jpn. 2004, 77: 909 -
20a
Brieger G.Nestrick TJ. Chem. Rev. 1974, 74: 567 -
20b
Johnstone RAW.Wilby AH.Entwistle ID. Chem. Rev. 1985, 85: 129 -
20c
Zassinovich G.Mestroni G.Gladiall S. Chem. Rev. 1992, 92: 1051 -
20d
Naota T.Takaya H.Murahashi S.-I. Chem. Rev. 1998, 98: 2599 -
20e
Carmona D.Lamata MP.Oro LA. Eur. J. Inorg. Chem. 2002, 2239 -
20f
Bäckvall J.-E. J. Organomet. Chem. 2002, 652: 105 - 21
Ley SV.Madin A. In Comprehensive Organic Synthesis Vol. 7:Trost BM.Fleming I. Pergamon; Oxford: 1991. p.251-289 - For example:
-
22a
Markó IE.Giles PR.Tsukazaki M.Brown SM.Urch CJ. Science 1996, 274: 2044 -
22b
Sato K.Aoki M.Takagi J.Noyori R. J. Am. Chem. Soc. 1997, 119: 12386 -
22c
Kakiuchi N.Maeda Y.Nishimura T.Uemura S. J. Org. Chem. 2001, 66: 6620 -
23a
Namy JL.Souppe J.Collin J.Kagan HB. J. Org. Chem. 1984, 49: 2045 -
23b
Ishii Y.Nakano T.Inada A.Kishigami Y.Sakurai K.Ogawa M. J. Org. Chem. 1986, 51: 240 -
23c
Wang G.-Z.Bäckvall J.-E. J. Chem. Soc., Chem. Commun. 1992, 337 -
23d
Krohn K.Knauer B.Küpke J.Seebach D.Beck AK.Hayakawa M. Synthesis 1996, 1341 -
23e
Almeida MLS.Beller M.Wang G.-Z.Bäckvall J.-E. Chem.-Eur. J. 1996, 2: 1533 -
23f
Hashiguchi S.Fujii A.Haack K.-J.Matsumura K.Ikariya T.Noyori R. Angew. Chem., Int. Ed. Engl. 1997, 36: 288 -
23g
Nishibayashi Y.Yamauchi A.Onodera G.Uemura S. J. Org. Chem. 2003, 68: 5875 -
23h
Gauthier S.Scopelliti R.Severin K. Organometallics 2004, 23: 3769 -
24a
Fujita K.Furukawa S.Yamaguchi R. J. Organomet. Chem. 2002, 649: 289 -
24b
Hanasaka F.Fujita K.Yamaguchi R. Organometallics 2004, 23: 1490 -
25a
Suzuki T.Morita K.Tsuchida M.Hiroi K. J. Org. Chem. 2003, 68: 1601 -
25b See also:
Suzuki T.Morita K.Tsuchida M.Hiroi K. Org. Lett. 2002, 4: 2361 -
25c
Suzuki T.Morita K.Matsuo Y.Hiroi K. Tetrahedron Lett. 2003, 44: 2003 - 26
Smith MB.March J. Advanced Organic Chemistry 5th ed.: Wiley; New York: 2001. p.499 - 27
Abdel-Magid AF.Carson KG.Harris BD.Maryanoff CA.Shah RD. J. Org. Chem. 1996, 61: 3849 -
28a
Watanabe Y.Tsuji Y.Ohsugi Y. Tetrahedron Lett. 1981, 22: 2667 -
28b
Murahashi S.-I.Kondo K.Hakata T. Tetrahedron Lett. 1982, 23: 229 -
28c
Watanabe Y.Tsuji Y.Ige H.Ohsugi Y.Ohta T. J. Org. Chem. 1984, 49: 3359 -
28d
Bitsi G.Schleiffer E.Antoni F.Jenner G. J. Organomet. Chem. 1989, 373: 343 -
28e
Watanabe Y.Morisaki Y.Kondo T.Mitsudo T. J. Org. Chem. 1996, 61: 4214 - 29
Grigg R.Mitchell TRB.Sutthivaiyakit S.Tongpenyai N. J. Chem. Soc., Chem. Commun. 1981, 611 - 30
Fujita K.Li Z.Ozeki N.Yamaguchi R. Tetrahedron Lett. 2003, 44: 2687 - 31
Comprehensive Heterocyclic Chemistry II
Bird CW. Pergamon; Oxford: 1996. -
32a
Hegedus LS. Angew. Chem., Int. Ed. Engl. 1988, 27: 1113 -
32b
Gilchrist TL. J. Chem. Soc., Perkin Trans. 1 1999, 2849 -
32c
Gribble GW. J. Chem. Soc., Perkin Trans. 1 2000, 1045 -
33a
Larock RC.Babu S. Tetrahedron Lett. 1987, 28: 5291 -
33b
Tsuji Y.Kotachi S.Huh K.-T.Watanabe Y. J. Org. Chem. 1990, 55: 580 -
33c
Hsu GC.Kosar WP.Jones WD. Organometallics 1994, 13: 385 -
33d
Kondo T.Okada T.Suzuki T.Mitsudo T. J. Organomet. Chem. 2001, 622: 149 -
33e
Tokunaga M.Ota M.Haga M.Wakatsuki Y. Tetrahedron Lett. 2001, 42: 3865 -
33f
Nakamura I.Yamamoto Y. Chem. Rev. 2004, 104: 2127 - 34
Larock RC.Berrios-Pena NG.Fried CA.Yum EK.Tu C.Leong W. J. Org. Chem. 1993, 58: 4509 - 35
Fujita K.Yamamoto K.Yamaguchi R. Org. Lett. 2002, 4: 2691 - 36
Fujita K.Takahashi Y.Owaki M.Yamamoto K.Yamaguchi R. Org. Lett. 2004, 6: 2785 -
37a
Corwin AH. In Heterocyclic Compounds Vol. 1:Elderfield RC. John Wiley and Sons Inc.; New York: 1950. p.277-342 -
37b
Mosher HS. In Heterocyclic Compounds Vol. 1:Elderfield RC. John Wiley and Sons Inc.; New York: 1950. p.617-676 -
37c
Baliah V.Jeyaraman R.Chandrasekaran L. Chem. Rev. 1983, 83: 379 -
37d
Bowman WR.Fletcher AJ.Potts GBS. J. Chem. Soc., Perkin Trans. 1 2002, 2747 -
38a
Tsuji Y.Huh K.-T.Ohsugi Y.Watanabe Y. J. Org. Chem. 1985, 50: 1365 -
38b
Tsuji Y.Yokoyama Y.Huh K.-T.Watanabe Y. Bull. Chem. Soc. Jpn. 1987, 60: 3456 -
38c
Felföldi K.Klyavlin MS.Bartók M. J. Organomet. Chem. 1989, 362: 193 -
38d
Abbenhuis RATM.Boersma J.van Koten G. J. Org. Chem. 1998, 63: 4282 -
38e
See also ref. 20d and 28b.
- 39
Fujita K.Fujii T.Yamaguchi R. Org. Lett. 2004, 6: 3525 - For example:
-
40a
Davis FA.Chao B.Fang T.Szewczyk JM. Org. Lett. 2000, 2: 1041 -
40b
Amat M.Llor N.Hidalgo J.Escolano C.Bosch J. J. Org. Chem. 2003, 68: 1919 - Asymmetric hydrogenation of cyclic imines catalyzed by transition metal complex with chiral ligand is another method for the synthesis of optically active cyclic amines:
-
41a
Willoughby CA.Buchwald SL. J. Am. Chem. Soc. 1994, 116: 8952 -
41b
Tang W.Zhang X. Chem. Rev. 2003, 103: 3029 - Synthesis of 1,2,3,4-tetrahydroquinoline derivatives by the reduction of quinolines:
-
42a
Hönel M.Vierhapper FW. J. Chem. Soc., Perkin Trans. 1 1980, 1933 -
42b
Fish RH.Tan JL.Thormodsen AD. J. Org. Chem. 1984, 49: 4500 -
42c
Fish RH.Tan JL.Thormodsen AD. Organometallics 1985, 4: 1743 -
42d
Sánchez-Delgado RA.González E. Polyhedron 1989, 8: 1431 -
42e
Murahashi S.-I.Imada Y.Hirai Y. Bull. Chem. Soc. Jpn. 1989, 62: 2968 -
42f
Baralt E.Smith SJ.Hurwitz J.Horváth IT.Fish RH. J. Am. Chem. Soc. 1992, 114: 5187 -
42g
Chin CS.Park Y.Lee B. Catal. Lett. 1995, 31: 239 -
42h
Wang W.-B.Lu S.-M.Yang P.-Y.Han X.-W.Zhou Y.-G. J. Am. Chem. Soc. 2003, 125: 10536 - 43
Fujita K.Kitatsuji C.Furukawa S.Yamaguchi R. Tetrahedron Lett. 2004, 45: 3215 - Recent reports on the catalytic application of Cp*Ir complexes:
-
44a
Cho J.-Y.Iverson CN.Smith MR. J. Am. Chem. Soc. 2000, 122: 12868 -
44b
Hou Z.Koizumi T.Fujita A.Yamazaki H.Wakatsuki Y. J. Am. Chem. Soc. 2001, 123: 5812 -
44c
Golden JT.Andersen RA.Bergman RG. J. Am. Chem. Soc. 2001, 123: 5837 -
44d
Ogo S.Makihara N.Kaneko Y.Watanabe Y. Organometallics 2001, 20: 4903 -
44e
Thorpe T.Blacker J.Brown SM.Bubert C.Crosby J.Fitzjohn S.Muxworthy JP.Williams JMJ. Tetrahedron Lett. 2001, 42: 4041 -
44f
Murata K.Konishi H.Ito M.Ikariya T. Organometallics 2002, 21: 253 -
44g
Klei SR.Golden JT.Tilley TD.Bergman RG. J. Am. Chem. Soc. 2002, 124: 2092 -
44h
Faller JW.Lavoie AR. Organometallics 2002, 21: 3493 -
44i
Carmona D.Lahoz FJ.Elipe S.Oro LA.Lamata MP.Viguri F.Sánchez F.Martínez S.Cativiela C.López-Ram de Víu MP. Organometallics 2002, 21: 5100 -
44j
Skaddan MB.Yung CM.Bergman RG. Org. Lett. 2004, 6: 11 -
44k
Himeda Y.Onozawa-Komatsuzaki N.Sugihara H.Arakawa H.Kasuga K. Organometallics 2004, 23: 1480 -
44l
Fujita K.Nonogawa M.Yamaguchi R. Chem. Commun. 2004, 1926