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Volumn , Issue 3, 2010, Pages 391-409

Regioselective reductive cross-coupling reactions of unsymmetrical alkynes

Author keywords

Alkenes; Alkynes; Carbometalation; Cross coupling; Reduction; Synthetic methods; Titanium

Indexed keywords


EID: 74549172880     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200901094     Document Type: Review
Times cited : (99)

References (177)
  • 1
    • 33747041670 scopus 로고    scopus 로고
    • For an interesting discussion in the context of process chemistry, see: T. Y. Zhang, Chem. Rev. 2006, 106, 2583-2595.
    • (2006) Chem. Rev. , vol.106 , pp. 2583-2595
    • Zhang, T.Y.1
  • 2
    • 0025649186 scopus 로고
    • For discussions regarding the "maturity" of organic chemistry as a scientific discipline, see: a) D. Seebach, Angew. Chem. Int. Ed. Engl. 1990, 29, 1320-1367;
    • (1990) Angew. Chem. Int. Ed. Engl. , vol.29 , pp. 1320-1367
    • Seebach, D.1
  • 12
    • 27544502994 scopus 로고    scopus 로고
    • For a review of metal catalyzed cycloisomerization
    • e) B. M. Trost, M. U. Frederiksen, M. T. Rudd, Angew. Chem. Int. Ed. 2005, 44, 6630-6666. For a review of metal catalyzed cycloisomerization, see:
    • (2005) Angew. Chem. Int. Ed. , vol.44 , pp. 6630-6666
    • Trost, B.M.1    Frederiksen, M.U.2    Rudd, M.T.3
  • 14
    • 11744317080 scopus 로고
    • For reviews of Zr-mediated processesg
    • For reviews of Zr-mediated processes, see: g) S. L. Buchwald, R. B. Nielsen, Chem. Rev. 1988, 88, 1047-1058;
    • (1988) Chem. Rev. , vol.88 , pp. 1047-1058
    • Buchwald, S.L.1    Nielsen, R.B.2
  • 20
    • 57149129735 scopus 로고    scopus 로고
    • For a recent review of Co- and Ni-catalyzed reductive coupling of alkyns, alienes and alkenes with alkenes, see: m) M. Jeganmohan, C.-H. Cheng, Chem. Eur. J. 2008, 14, 10876-10886.
    • (2008) Chem. Eur. J. , vol.14 , pp. 10876-10886
    • Jeganmohan, M.1    Cheng, C.-H.2
  • 26
    • 0000803017 scopus 로고
    • For early discussions concerning the reversibility of metallacyclopentane formation, see: a) J. X. McDermott, G. M. Whitesides, J. Am. Chem. Soc. 1974, 96, 947-948;
    • (1974) J. Am. Chem. Soc. , vol.96 , pp. 947-948
    • McDermott, J.X.1    Whitesides, G.M.2
  • 29
    • 33845185445 scopus 로고
    • For an example of regioselective reductive coupling where thermodynamic equilibration of a mixture of metallacyclopentadienes leads to selective formation of a regiodefined 1,3-diene, see: d) S. L. Buchwald, R. B. Nielsen, J. Am. Chem. Soc. 1989, 111, 2870-2874.
    • (1989) J. Am. Chem. Soc. , vol.111 , pp. 2870-2874
    • Buchwald, S.L.1    Nielsen, R.B.2
  • 30
    • 0041851126 scopus 로고    scopus 로고
    • For an example of a silyl-alkyne in regioselective Alder-ene chemistry, see: a) B. M. Trost, M. R. Machacek, Z. T. Ball, Org. Lett. 2003, 5, 1895-1898.
    • (2003) Org. Lett. , vol.5 , pp. 1895-1898
    • Trost, B.M.1    Machacek, M.R.2    Ball, Z.T.3
  • 31
    • 14944376621 scopus 로고    scopus 로고
    • For an example of regioselective Alder-ene chemistry with alkynylboronates, see: b) E. C. Hansen, D. Lee, J. Am. Chem. Soc. 2005, 127, 3252-3253.
    • (2005) J. Am. Chem. Soc. , vol.127 , pp. 3252-3253
    • Hansen, E.C.1    Lee, D.2
  • 35
    • 0001588941 scopus 로고
    • For an example of a Ta-mediated regioselective reductive coupling of alkynes with aldehydes where regioselectivity is derived from C-C bond formation distal to a TMS- or t Bu substituent, see: b) K. Takai, Y. Kataoka, K. Utimoto, J. Org. Chem. 1990, 55, 1707-1708.
    • (1990) J. Org. Chem. , vol.55 , pp. 1707-1708
    • Takai, K.1    Kataoka, Y.2    Utimoto, K.3
  • 36
    • 0002015261 scopus 로고    scopus 로고
    • For a regioselective reductive cross-coupling of a stannylalkyne with an aldehyde, see: c) V. Launay, I. Beaudet, J.-P. Quintard, Synlett 1997, 821-823.
    • (1997) Synlett , pp. 821-823
    • Launay, V.1    Beaudet, I.2    Quintard, J.-P.3
  • 44
    • 0004496618 scopus 로고
    • For a study of regioselective Ta-mediated reductive coupling of acetylenic esters and amides with carbonyl compounds, see: K. Takai, M. Tezuka, K. Utimoto, J. Org. Chem. 1991, 56, 5980-5982.
    • (1991) J. Org. Chem. , vol.56 , pp. 5980-5982
    • Takai, K.1    Tezuka, M.2    Utimoto, K.3
  • 53
    • 61449131532 scopus 로고    scopus 로고
    • For an example in silacyclopropane-mediated coupling of alkynes with nitriles, see: L. L. Anderson, K. A. Woerpel, Org. Lett. 2009, 11, 425-428.
    • (2009) Org. Lett. , vol.11 , pp. 425-428
    • Anderson, L.L.1    Woerpel, K.A.2
  • 54
  • 55
    • 0037123793 scopus 로고    scopus 로고
    • For a range of selectivities observed in Ru-catalyzed Alder-ene chemistry, see: b) B. M. Trost, H. C. Shen, A. B. Pinkerton, Chem. Eur. J. 2002, 8, 2341-2349.
    • (2002) Chem. Eur. J. , vol.8 , pp. 2341-2349
    • Trost, B.M.1    Shen, H.C.2    Pinkerton, A.B.3
  • 56
    • 0028934739 scopus 로고
    • An interesting exception to this trend was reported in the Tialkoxide promoted reductive cross-coupling of an phenylpropyne with cyclohexanecarboxaldehyde: a) K. Harada, H. Urabe, F. Sato, Tetrahedron Lett. 1995, 36, 3203-3206.
    • (1995) Tetrahedron Lett. , vol.36 , pp. 3203-3206
    • Harada, K.1    Urabe, H.2    Sato, F.3
  • 57
    • 0029146881 scopus 로고
    • Surprisingly, this selectivity was reported to be reversed in these authors study of a Ti-alkoxide-mediated reductive cross-coupling of the same alkyne with an imine, see: b) Y. Gao, K. Harada, F. Sato, Tetrahedron Lett. 1995, 36, 5913-5916.
    • (1995) Tetrahedron Lett. , vol.36 , pp. 5913-5916
    • Gao, Y.1    Harada, K.2    Sato, F.3
  • 61
    • 0000818126 scopus 로고
    • While not included in the discussion due to the highly focused nature of this review, regioselective coupling reactions of other heteroatom-substituted alkynes have been reported. For RSsubstitution, see: a) B. C. Van Wagenen, T. Livinghouse, Tetrahedron Lett. 1989, 30, 3495-3498;
    • (1989) Tetrahedron Lett. , vol.30 , pp. 3495-3498
    • Van Wagenen, B.C.1    Livinghouse, T.2
  • 65
    • 0141739766 scopus 로고    scopus 로고
    • For RP-based substitution, see: e) A. Quntar, M. Srebnik, Org. Lett. 2003, 5, 357-359.
    • (2003) Org. Lett. , vol.5 , pp. 357-359
    • Quntar, A.1    Srebnik, M.2
  • 66
    • 74549178258 scopus 로고    scopus 로고
    • [l4].
    • [l4].
  • 72
    • 74549156654 scopus 로고    scopus 로고
    • [5k]
    • [5k],
  • 73
    • 74549206477 scopus 로고    scopus 로고
    • [51] and
    • [51] and
  • 75
    • 0000458209 scopus 로고
    • For a review of substrate-directable reactions in organic chemistry, see: A. H. Hoveyda, D. A. Evans, G. C. Fu, Chem. Rev. 1993, 93, 1307-1370.
    • (1993) Chem. Rev. , vol.93 , pp. 1307-1370
    • Hoveyda, A.H.1    Evans, D.A.2    Fu, G.C.3
  • 86
    • 0000243839 scopus 로고    scopus 로고
    • For directed carbometalation based on aluminum/zirconium, see: k) S. Ma, E.-I. Negishi, J. Org. Chem. 1997, 62, 784-785.
    • (1997) J. Org. Chem. , vol.62 , pp. 784-785
    • Ma, S.1    Negishi, E.-I.2
  • 87
    • 0001247486 scopus 로고
    • For examples of S- and P-directed C-C bond formation, see: a) S. D. Burke, J. E. Cobb, Tetrahedron Lett. 1986, 27, 4237-4240;
    • (1986) Tetrahedron Lett. , vol.27 , pp. 4237-4240
    • Burke, S.D.1    Cobb, J.E.2
  • 93
    • 47749098988 scopus 로고    scopus 로고
    • For an interesting approach to relay transient formation of a C-O bond to P-directed hydroformylation, see: g) T. E. Lightburn, M. T. Dombrowski, K. L. Tan, J. Am. Chem. Soc. 2008, 130, 9210-9211.
    • (2008) J. Am. Chem. Soc. , vol.130 , pp. 9210-9211
    • Lightburn, T.E.1    Dombrowski, M.T.2    Tan, K.L.3
  • 100
    • 77349090183 scopus 로고    scopus 로고
    • DOI: 10.1021/cr900005n.
    • For a recent review of Rh-catalyzed C-C bond formation via heteroatom-directed C-H bond activation, see: f) D. A. Colby, R. G. Bergman, J. A. Ellman, Chem. Rev. 2009, DOI: 10.1021/cr900005n.
    • (2009) Chem. Rev.
    • Colby, D.A.1    Bergman, R.G.2    Ellman, J.A.3
  • 125
    • 74549168184 scopus 로고    scopus 로고
    • The calculation presented in Figure 12 is based on the use of 5-10 mol-% of each catalyst (as reported in the literature for typical catalytic processes). The cost associated with additional reagents for these processes has not been considered in calculations presented. That said, the current cost of 2 mol of iPrMgCl is approximately $184 whereas the additional cost associated with use of 5mol-% of (+/-)-BIPHEP is $1,359 (Strem-2008).
    • The calculation presented in Figure 12 is based on the use of 5-10 mol-% of each catalyst (as reported in the literature for typical catalytic processes). The cost associated with additional reagents for these processes has not been considered in calculations presented. That said, the current cost of 2 mol of iPrMgCl is approximately $184 whereas the additional cost associated with use of 5mol-% of (+/-)-BIPHEP is $1,359 (Strem-2008).
  • 126
    • 74549225400 scopus 로고    scopus 로고
    • 4 for a hypothetical reaction run on 1-mol scale would cost approximately $220 Strem 2008
    • 4 for a hypothetical reaction run on 1-mol scale would cost approximately $220 (Strem 2008).
  • 127
    • 74549164529 scopus 로고    scopus 로고
    • 4, and no significant precautions need to be taken to exclude trace quantities of air or water from the reaction mixture
    • 4, and no significant precautions need to be taken to exclude trace quantities of air or water from the reaction mixture.
  • 128
    • 0037124795 scopus 로고    scopus 로고
    • For an early report of a directed Kulinkovich reaction that embraced a potential bicyclic metallacyclopropane as an intermediate; see: L. G. Quan, S.-H. Kim, J. C Lee, J. K. Cha, Angew. Chem. Int. Ed. 2002, 41, 2160-2162.
    • (2002) Angew. Chem. Int. Ed. , vol.41 , pp. 2160-2162
    • Quan, L.G.1    Kim, S.-H.2    Lee, J.C.3    Cha, J.K.4
  • 129
    • 0346786924 scopus 로고
    • For an early report of a related design in Ta-mediated reductive coupling that was limited to the reaction of internal alkynes with terminal alkenes, see: K. Takai, M. Yamada, H. Odaka, K. Utimoto, J. Org. Chem. 1994, 59, 5852-5853.
    • (1994) J. Org. Chem. , vol.59 , pp. 5852-5853
    • Takai, K.1    Yamada, M.2    Odaka, H.3    Utimoto, K.4
  • 130
    • 74549122795 scopus 로고    scopus 로고
    • Regiochemical control in alkyne functionalization was not achieved as a result of the preorganization envoked. Rather, reactivity of a preformed monocyclic Ta-alkyne complex was achieved with a terminal alkene containing a tethered hydroxy substituent. Also, the position of the hydroxy substituent played a central role in the site-selective reaction of dienes with a preformed Ta-alkyne complex.
    • Regiochemical control in alkyne functionalization was not achieved as a result of the preorganization envoked. Rather, reactivity of a preformed monocyclic Ta-alkyne complex was achieved with a terminal alkene containing a tethered hydroxy substituent. Also, the position of the hydroxy substituent played a central role in the site-selective reaction of dienes with a preformed Ta-alkyne complex.
  • 131
    • 74549208837 scopus 로고    scopus 로고
    • While the use of substituted alkenes, allenes and alkynes are well known in intramolecular metallacycle-mediated bond construction, barriers associated with reactivity broadly impact the viability of such bond constructions in a bimolecular manifold.
    • While the use of substituted alkenes, allenes and alkynes are well known in intramolecular metallacycle-mediated bond construction, barriers associated with reactivity broadly impact the viability of such bond constructions in a bimolecular manifold.
  • 134
    • 36549023143 scopus 로고    scopus 로고
    • For selected examples of carbonyl olefination for the stereoselective generation of 1,3-dienes in the context of natural product total synthesis, see: c) S. Bonazzi, S. Güttinger, I. Zemp, U. Kutay, K. Gademann, Angew. Chem. Int. Ed, 2007, 46, 8707-8710;
    • (2007) Angew. Chem. Int. Ed , vol.46 , pp. 8707-8710
    • Bonazzi, S.1    Güttinger, S.2    Zemp, I.3    Kutay, U.4    Gademann, K.5
  • 142
    • 2042507954 scopus 로고
    • For reviews of palladium-catalyzed cross-coupling, see: a) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483;
    • (1995) Chem. Rev. , vol.95 , pp. 2457-2483
    • Miyaura, N.1    Suzuki, A.2
  • 145
    • 4544263102 scopus 로고    scopus 로고
    • For selected examples of metal-mediated cross-coupling for the assembly of dienes in the context of natural product synthesis, see: d) N. F. Langille, J. S. Panek, Org. Lett. 2004, 6, 3203-3206;
    • (2004) Org. Lett. , vol.6 , pp. 3203-3206
    • Langille, N.F.1    Panek, J.S.2
  • 149
    • 74549195308 scopus 로고    scopus 로고
    • [7d,21]. Also, for a summary of previously required substitution patterns of the internal alkyne to render this type of reductive cross-coupling reaction regioselective, see Figure 10 and the accompanying discussion.
    • [7d,21]. Also, for a summary of previously required substitution patterns of the internal alkyne to render this type of reductive cross-coupling reaction regioselective, see Figure 10 and the accompanying discussion.
  • 154
    • 0003913629 scopus 로고    scopus 로고
    • J. Otera (Ed.), Wiley-VCH, Weinheim
    • J. Otera (Ed.), Modern Carbonyl Chemistry, Wiley-VCH, Weinheim, 2000.
    • (2000) Modern Carbonyl Chemistry
  • 161
    • 0000288714 scopus 로고
    • In the reaction of a Ti-alkyne complex with a carbonyl electrophile, conversion of the metallacyclopropene species to the metallacyclopentene intermediate is coupled to the formation of a strong Ti-O bond. In the related reaction with an alkyne, formation of the metallacyclopentadiene is coupled to the formation of a relatively weak Ti-C bond. For a discussion of the relative position of transition states as a function of the relative exothermicity of the reaction, see: a
    • In the reaction of a Ti-alkyne complex with a carbonyl electrophile, conversion of the metallacyclopropene species to the metallacyclopentene intermediate is coupled to the formation of a strong Ti-O bond. In the related reaction with an alkyne, formation of the metallacyclopentadiene is coupled to the formation of a relatively weak Ti-C bond. For a discussion of the relative position of transition states as a function of the relative exothermicity of the reaction, see: a) J. E. Leffier, Science 1953, 117, 340-341;
    • (1953) Science , vol.117 , pp. 340-341
    • Leffier, J.E.1
  • 170
    • 74549155420 scopus 로고    scopus 로고
    • For an allylic alcohol-alkyne coupling, see:
    • For an allylic alcohol-alkyne coupling, see:
  • 175
    • 63149167445 scopus 로고    scopus 로고
    • For examples of complex Ti-mediated reductive cross-coupling reactions in the synthesis of natural products, see: a) T. K. Macklin, G. C. Micalizio, J. Am. Chem. Soc. 2009, 131, 1392-1393;
    • (2009) J. Am. Chem. Soc. , vol.131 , pp. 1392-1393


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