Subscribe to RSS
DOI: 10.1055/s-2003-43334
New Advances in Selected Transition Metal-Catalyzed Annulations
Publication History
Publication Date:
07 November 2003 (online)
![](https://www.thieme-connect.de/media/synlett/200315/lookinside/thumbnails/10.1055-s-2003-43334-1.jpg)
Abstract
This account describes the recent advances on the Pd-catalyzed [4+2]-benzannulation reaction, development of chemo- and regiospecific formal [2+2+2]-cyclotrimerization of alkynes, as well as discovery and evolution of the transition metal-catalyzed cycloisomerization of alkynyl ketones and imines into five-membered heteroaromatics.
-
1 Advances in Pd-Catalyzed Benzannulation Reactions
-
1.1 Introduction
-
1.2 Formal [2+2+2]-Trimerization of Alkynes
-
1.3 Acceleration of Benzannulation Reaction by Lewis Acids
-
1.4 Regioselectivity of the Benzannulation with Unsymmetrical Diynes
-
1.5 Palladium-Catalyzed Head-to-Head Coupling of Alkynes
-
1.6 Palladium-Catalyzed Cross-Coupling of Alkynes with Allenes
-
2 Novel Transition Metal-Catalyzed Cycloisomerization Reactions
-
2.1 Introduction
-
2.2 Cu-Catalyzed Cycloisomerization of Alkynyl Imines into Pyrroles
-
2.3 Cycloisomerization of Alkynyl Ketones into Furans
-
2.4 Investigation of the Mechanism of the Cu-Catalyzed Cycloisomerization Reaction
-
2.5 Formation of Unexpected Bicyclic Product
-
2.6 Multi-Substituted Heterocycles
-
2.6.1 Towards 3-Substituted Heterocycles
-
2.6.2 4-Substituted Heterocycles via 1,2-Migrations
-
2.6.3 Tetrasubstituted Furans
-
2.7 Fused Pyrroloheterocycles
-
2.8 Application of the Cycloisomerization Reaction to Synthesis of Alkaloid Structures
-
3 Conclusion
Key words
transition metal catalysis - benzannulation - cycloisomerization - cascade reactions - fused heteroaromatics
- 1 For the first report see:
Saito S.Salter MM.Gevorgyan V.Tsuboya N.Tando K.Yamamoto Y. J. Am. Chem. Soc. 1996, 118: 3970 - For reviews see:
-
2a
Gevorgyan V.Yamamoto Y. J. Organomet. Chem. 1999, 576: 232 -
2b
Saito S.Yamamoto Y. Chem. Rev. 2000, 100: 2901 -
2c
Saito S.Yamamoto Y. Palladium-Catalyzed Benzannulation Reactions of Conjugated Enynes and Diynes In Handbook of Organopalladium Chemistry for Organic SynthesisNegishi E. Wiley; New York: 2002. - 4
Danheiser RL.Gould AE.de la Pradilla RF.Helgason AL. J. Org. Chem. 1994, 59: 5514 - 5
Gevorgyan V.Takeda A.Homma M.Sadayori N.Radhakrishnan U.Yamamoto Y. J. Am. Chem. Soc. 1999, 121: 6391 - 6
Gevorgyan V.Tando K.Uchiyama N.Yamamoto Y. J. Org. Chem. 1998, 63: 7022 - 7
Lewis FD.Zuo X.Gevorgyan V.Rubin M. J. Am. Chem. Soc. 2002, 124: 13664 -
9a
Saito S.Tsuboya N.Chounan Y.Nogami T.Yamamoto Y. Tetrahedron Lett. 1999, 40: 7529 -
9b
Saito S.Chounan Y.Nogami T.Fukushi T.Tsuboya N.Yamada Y.Kitahara H.Yamamoto Y. J. Org. Chem. 2000, 65: 5350 - 10
Saito S.Ohmori O.Yamamoto Y. Org. Lett. 2000, 2: 3853 ; see also corrigendum Org. Lett. 2001, 3, 493 - 11
Gevorgyan V.Quan LG.Yamamoto Y. J. Org. Chem. 1998, 63: 1244 - 12
Gevorgyan V.Quan LG.Yamamoto Y. J. Org. Chem. 2000, 65: 568 - 13
Saito S.Uchiyama N.Gevorgyan V.Yamamoto Y. J. Org. Chem. 2000, 65: 4338 - 14
Rubin M.Markov J.Chuprakov S.Wink DJ.Gevorgyan V. J. Org. Chem. 2003, 68: 6251 - 15
Gevorgyan V.Tsuboya N.Yamamoto Y. J. Org. Chem. 2001, 66: 2743 - 16
Saito S.Tsuboya N.Yamamoto Y. J. Org. Chem. 1997, 62: 5042 - 17
Weibel D.Gevorgyan V.Yamamoto Y. J. Org. Chem. 1998, 63: 1217 - 18
Liu JX.Saito S.Yamamoto Y. Tetrahedron Lett. 2000, 41: 4201 - 19
Kawasaki T.Saito S.Yamamoto Y. J. Org. Chem. 2002, 67: 2653 - 20
Kawasaki T.Yamamoto Y. J. Org. Chem. 2002, 67: 5138 - 21
Hegedus LS. Transition Metals in the Synthesis of Complex Organic Molecules 2nd Ed.: University Science Books; Sausalito: 1999. -
22a
Ozerov OV.Ladipo FT.Patrick BO. J. Am. Chem. Soc. 1999, 121: 7941 -
22b
Ozerov OV.Patrick BO.Ladipo FT. J. Am. Chem. Soc. 2000, 122: 6423 - 23 For recent review see:
Aubert C.Buisine O.Petit M.Slowinski F.Malacria M. Pur. Appl. Chem. 1999, 71: 1463 - 24
Vollhardt KPC. Angew. Chem., Int. Ed. Engl. 1984, 23: 539 -
25a
Eichberg MJ.Dorta RL.Grotjahn DB.Lamottke K.Schmidt M.Vollhardt KPC. J. Am. Chem. Soc. 2001, 123: 9324 -
25b
Funk RL.Vollhardt KPC. J. Am. Chem. Soc. 1979, 101: 215 -
25c
Saa C.Crotts DD.Hsu G.Vollhardt KPC. Synlett 1994, 487 - See for example:
-
26a
Bruns D.Miura H.Vollhardt KPC.Stanger A. Org. Lett. 2003, 5: 549 -
26b
Han S.Anderson DR.Bond AD.Chu HV.Disch RL.Holmes D.Schulman JM.Teat SJ.Vollhardt KPC.Whitener GD. Angew. Chem. Int. Ed. 2002, 41: 3227 -
26c
Dosa PI.Whitener GD.Vollhardt KPC.Bond AD.Teat SJ. Org. Lett. 2002, 4: 2075 - 27 For direct proof of involvement of metallacyclopentadienyl intermediate see:
Diercks R.Eaton BE.Gürtzgen S.Jalisatgi S.Matzger AJ.Radde RH.Vollhardt KPC. J. Am. Chem. Soc. 1998, 120: 8247 -
28a
Takahashi T.Xi Z.Yamazaki A.Liu Y.Nakajima K.Kotora M. J. Am. Chem. Soc. 1998, 120: 1672 -
28b
Takahashi T.Tsai F.-Y.Li Y.Nakajima K.Kotora M. J. Am. Chem. Soc. 1999, 121: 11093 -
29a
Suzuki D.Urabe H.Sato F. J. Am. Chem. Soc. 2001, 123: 7925 -
29b
Tanaka R.Nakano Y.Suzuki D.Urabe H.Sato F. J. Am. Chem. Soc. 2002, 124: 9683 - 30
Trost BM.Sorum MT.Chan C.Harms AE.Ruhter G. J. Am. Chem. Soc. 1997, 119: 698 - 31
Gevorgyan V.Radhakrishnan U.Takeda A.Rubina M.Rubin M.Yamamoto Y. J. Org. Chem. 2001, 66: 2835 - 34
Rubina M.Gevorgyan V. J. Am. Chem. Soc. 2001, 123: 11107 - 35 For Pd(0)-TDMPP series see Supporting Information for Ref. For Pd(II)-TDMPP series see:
Kurosawa H.Tsuboi A.Kawasaki Y.Wada M. Bull. Chem. Soc. Jpn. 1987, 60: 3563 - For most recent reviews on Ru-catalyzed dimerization see:
-
36a
Trost BM.Toste FD.Pinkerton A. Chem. Rev. 2001, 101: 2067 -
36b
Bruneau C.Dixneuf PH. Acc. Chem. Res. 1999, 32: 311 -
36c For M = Co, Rh see:
Field LD.Ward AJ.Turner P. Aust. J. Chem. 1999, 52: 1085 -
36d For M = Ir see:
Ohmura T.Yorozuya S.Yamamoto Y.Miyaura N. Organometallics 2000, 19: 365 -
36e For M = Ti see:
Akita M.Yasuda H.Nakamura A. Bull. Chem. Soc. Jpn. 1984, 57: 480 -
37a For M = Y see:
Duchateau R.van Wee CT.Teuben JH. Organometallics 1996, 15: 2291 -
37b For M = Lu see:
Nishiura M.Hou ZM.Wakatsuki Y.Yamaki T.Miyamoto T. J. Am. Chem. Soc. 2003, 125: 1184 -
37c For M = Th, U see:
Haskel A.Straub T.Dash AK.Eisen MS. J. Am. Chem. Soc. 1999, 121: 3014 - 38
Ishikawa M.Ohshita J.Ito Y.Minato A. J. Organomet. Chem. 1988, 346: C58 - 39
Herrmann W.Bohm V.Gstottmayr C.Grosche M.Reisinger C.-P.Weskamp T. J. Organomet. Chem. 2001, 617-618: 616 - 40 For additional stabilization of transition metal complexes caused by agostic coordination of ortho-hydrogen atoms of an aryl ring to a metal center see for example:
Crabtree RH. Angew. Chem., Int. Ed. Engl. 1993, 32: 789 -
41a For M = Rh see:
Yamaguchi M.Omata K.Hirama M. Tetrahedron Lett. 1994, 35: 5689 -
41b For M = Ru see:
Yamaguchi M.Kido Y.Omata K.Hirama M. Synlett 1995, 1181 -
41c For M = Pd see:
Trost BM.Kottirsch G. J. Am. Chem. Soc. 1990, 112: 2816 - 42
Ma S.Xie H.Wang G.Zhang J.Shi Z. Synthesis 2001, 713 -
43a
In earlier works Trost proposed that catalytic system Pd(OAc)2-TDMPP works in the Pd(II)-Pd(IV) manifold. We believe that it is unlikely that Pd(II) species can survive in the presence of several reducing agents such as terminal alkynes and phosphines present in the reaction mixture. The tendency for Pd(II) to be easily reduced into Pd(0) species under a variety of reaction conditions is well known. See: Handbook of Organopalladium Chemistry for Organic Synthesis, Negishi, E., Ed.; John Wiley & Sons Inc.: Hoboken N.J., 2002.
-
43b
In addition our test experiments indicated that Pd2dba3/o-Tol3P combination works as selectively as Pd(OAc)2-TDMPP system albeit a bit slower to provide endo-enynes 41. Furthermore it also was shown by Trost and by us that Pd(0) complexes enable catalysis of head-to-tail homo- and cross-coupling of alkynes.
- See for example:
-
45a
Yamamoto Y.Ogawa R.Itoh K. J. Am. Chem. Soc. 2001, 123: 6189 -
45b
Fatland AW.Eaton BE. Org. Lett. 2000, 2: 3131 -
45c
Varela JA.Castedo L.Saa C. Org. Lett. 1999, 1: 2141 -
45d
Varela JA.Castedo L.Saa C. J. Am. Chem. Soc. 1998, 120: 12147 - 46
Kreher R. In Houben-Weyl, Methoden der organischen Chemie 4th Ed., Vol. E6A: Thieme; Stuttgart: 1994. p.556 - 47
Boger DL.Boyce CW.Labroli MA.Sehon CA.Jin Q. J. Am. Chem. Soc. 1999, 121: 54 -
48a
Schulte KE.Reisch J.Walker H. Arch. Pharm. 1965, 298: 98 -
48b
Chalk AJ. Tetrahedron Lett. 1972, 13: 3487 - 49
Green TW.Wuts PGM. Protective Groups in Organic Synthesis Wiley; New York: 1999. 3rd Ed.. - 50
Kel’in AV.Sromek AW.Gevorgyan V. J. Am. Chem. Soc. 2001, 123: 2074 - 51
Lin S.Sheng H.Huang Y. Synthesis 1991, 3: 235 -
52a
Sheng H.Lin S.Huang YZ. Tetrahedron Lett. 1986, 27: 4893 -
52b
Jeevanandam A.Narkunan K.Cartwright C.Ling Y.-C. Tetrahedron Lett. 1999, 40: 4841 - 53
Sheng H.Lin S.Huang YZ. Synthesis 1987, 1022 - 54
Marshall JA.Wang X.-J. J. Org. Chem. 1992, 57: 3387 - 55
Kel"in AV.Gevorgyan V. J. Org. Chem. 2002, 67: 95 -
57a
Ried W.Winkler H. Chem. Ber. 1979, 112: 384 -
57b
Ried W.Weidemann P. Chem. Ber. 1971, 104: 3329 -
57c
Himbert G.Schwickerath W. Liebigs Ann. Chem. 1984, 85 -
57d
Kelly TR.Maguire MP. Tetrahedron 1985, 41: 3033 -
57e
Linderman RJ.Kirollos KS. Tetrahedron Lett. 1990, 31: 2689 - It turned out that analogous structure cores have been previously reported in the literature.
-
58a
Brandsma L.Nedolya NA.Heerma V.Van der Kerk ASHTM.Lutz ETHG.de Lang R.-J.Afonin AV.Trofimov BA. Chem. Heterocycl. Compd. 1997, 33: 493 -
58b
Brandsma L.Nedolya NA.Verkruijsse HD.Owen NL.Li D.Trofimov BA. Tetrahedron Lett. 1997, 38: 6905 -
58c
Trofimov BA.Nedolya NA.Brandsma L.Frolov YuL.Larionova EYu.Toryashinova DD.Kobychev VB.Vitkovskaya NM. Sulfur Lett. 1999, 22: 249 - 59
Oelberg DG.Schiavelli MD. J. Org. Chem. 1977, 42: 1804 - 60
Saalfrank RW.Welch A.Haubner M.Bauer U. Liebigs Ann. 1996, 171 - 62
Kim JT.Kel’in AV.Gevorgyan V. Angew. Chem. Int. Ed. 2003, 42: 98 -
63a
Johnston BD.Pinto BM. J. Org. Chem. 2000, 65: 4607 -
63b
Yu B.Yang Z. Org. Lett. 2001, 3: 377 -
63c
Viso A.Poopeiko N.Castillon S. Tetrahedron Lett. 2000, 41: 407 -
64a
Plate R.Nivard RJF.Ottenheijm HCJ. Tetrahedron 1986, 42: 4503 -
64b
Hamel P. J. Org. Chem. 2002, 67: 2854 -
64c
Volonterio A.Zanda M.Bravo P.Fronza G.Cavicchio M.Crucianelli M. J. Org. Chem. 1997, 62: 8031 -
65a
Mahrwald R.Schick H. Angew. Chem., Int. Ed. Engl. 1991, 30: 593 -
65b
Kato K.Yamamoto Y.Akita H. Tetrahedron Lett. 2002, 43: 6587 - Phosphates:
-
66a
Nicolaou KC.Shi G.-Q.Namoto K. Chem. Commun. 1998, 16: 1757 -
66b
Nicolaou KC.Shi G.-Q.Gunzner JL.Gaertner P.Yang Z. J. Am. Chem. Soc. 1997, 119: 5467 -
66c Tosylates:
Roy AH.Hartwig JF. J. Am. Chem. Soc. 2003, 125: 8704 - 68
Daly JW. Science 1983, 705 - 69
Jefford CW.Tang Q.Zaslona A. Helv. Chim. Acta 1989, 72: 1749 -
70a
Merlin P.Braekman JC.Daloze D.Pasteels JM. J. Chem. Ecol. 1988, 14: 517 -
70b
Braekman JC.Daloze D.Pasteels JM.Vanhecke P.Declercq JP.Sinnwell V.Franke W. Z. Naturforsch., C: Biosci. 1987, 42: 627 - 71
Kim JT.Gevorgyan V. Org. Lett. 2002, 4: 4697
References
See for discussion of alternative mechanisms ref. [2c]
8Gevorgyan. V. Kel’in. A. V. Unpublished results.
32Conley, M.; Rubina, M.; Gevorgyan, V. unpublished results.
33Rubin, M.; Gevorgyan, V. unpublished results.
44Significant deuterium scrambling between deuterated terminal alkynes and eventual proton sources in the presence of transition metals is well documented.
56Sromek, A. W.; Gevorgyan, V. unpublished results.
61Sromek, A. W.; Yap, D.; Kel’in, A. V.; Gevorgyan, V. unpublished results.
67Park, C. H.; Gevorgyan, V. unpublished results.
72Kim, J. T.; Butt, J. R.; Gevorgyan, V. unpublished results.