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1
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For a seminal work on titanocene(III) chemistry see: T. V. Rajan Babu, W. A. Nugent, J. Am. Chem. Soc. 1994, 116, 986-997.
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For a seminal work on titanocene(III) chemistry see: T. V. Rajan Babu, W. A. Nugent, J. Am. Chem. Soc. 1994, 116, 986-997.
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2
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33746073438
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Recent reviews: a
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a) W. Oppolzer in Comprehensive Organic Synthesis, Vol. 5 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxfod, 1991, chap. 1.2;
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W . Oppolzer, M. Bedoya-Zurita, C. Y. Switzer, Tetrahedron Lett. 1988, 29, 6433-6436.
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54749138104
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For experimental details see Supporting Information
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For experimental details see Supporting Information.
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18
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54749144680
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Addition of triphenylphosphine considerably increased the yields, possibly stabilizing palladium intermediates
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Addition of triphenylphosphine considerably increased the yields, possibly stabilizing palladium intermediates.
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19
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54749129049
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The anti configuration of 2 was tentatively assigned on the basis of the stereochemical behavior evident in the closely related allylation of decanal with (E)-but-2-enyl ethyl carbonate promoted by Pd/Ti (Table 1, entry 11).
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The anti configuration of 2 was tentatively assigned on the basis of the stereochemical behavior evident in the closely related allylation of decanal with (E)-but-2-enyl ethyl carbonate promoted by Pd/Ti (Table 1, entry 11).
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0000337182
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W . Oppolzer, T. H. Keller, M. Bedoya-Zurita, C. Stone, Tetrahedron Lett. 1989, 30, 5883-5886.
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W . Oppolzer, T. H. Keller, M. Bedoya-Zurita, C. Stone, Tetrahedron Lett. 1989, 30, 5883-5886.
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Selected references: a T. Tabuchi, J. Inanaga, M. Yamaguchi, Tetrahedron Lett. 1986, 27, 1195-1196;
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Selected references: a) T. Tabuchi, J. Inanaga, M. Yamaguchi, Tetrahedron Lett. 1986, 27, 1195-1196;
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a) K. Yasui, Y. Goto, T. Yajima, Y. Taniseki, K. Fugami, A. Tanaka, Y. Tamaru, Tetrahedron Lett. 1993, 34, 7619-7622;
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30
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54749096019
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III-promoted Wurtz-type reaction of farnesyl ethyl carbonate, obtaining squalene (81%) with acceptable regio- and stereoselectivity. For details, see Supporting Information.
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III-promoted Wurtz-type reaction of farnesyl ethyl carbonate, obtaining squalene (81%) with acceptable regio- and stereoselectivity. For details, see Supporting Information.
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31
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0000334212
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For selected references of closely related nucleophilic allyltitanium complexes: a
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For selected references of closely related nucleophilic allyltitanium complexes: a) A. Kasatkin, T. Nakagawa, S. Okamoto, F. Sato, J. Am. Chem. Soc. 1995, 117, 3881-3882;
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b) F. Sato, S. Iijima, M. Sato, Tetrahedron Lett. 1981, 22, 243-246.
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37049089453
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In any case, alternative mechanisms based on nucleophilic allylpalladium complexes cannot be completely ruled out; see: a H. Nakamura, N. Asao, Y. Yamamoto, J. Chem. Soc. Chem. Commun. 1995, 1273-1274;
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In any case, alternative mechanisms based on nucleophilic allylpalladium complexes cannot be completely ruled out; see: a) H. Nakamura, N. Asao, Y. Yamamoto, J. Chem. Soc. Chem. Commun. 1995, 1273-1274;
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d) Review: G. Zanoni, A. Pontiroli, A. Marchetti, G. Vidari, Eur. J. Org. Chem. 2007, 3599-3611.
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37
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2442609566
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Exoc yclic alkene 4 is reminiscent of products obtained in the Oppolzer cyclization. It should be noted, however, that nickel catalysts have seldom been used for this transformation, possibly because it is not easy to reintroduce them into a catalytic cycle; see: B.-L. Lin, L. Liu, Y. Fu, S.-W. Luo, Q. Chen, Q.-X. Guo, Organometallics 2004, 23, 2114-2123.
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Exoc yclic alkene 4 is reminiscent of products obtained in the Oppolzer cyclization. It should be noted, however, that nickel catalysts have seldom been used for this transformation, possibly because it is not easy to reintroduce them into a catalytic cycle; see: B.-L. Lin, L. Liu, Y. Fu, S.-W. Luo, Q. Chen, Q.-X. Guo, Organometallics 2004, 23, 2114-2123.
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38
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0000159852
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This excellent stereoselectivity is considerably higher than that reported for related cyclizations based on titanium(II) and zirconium(II, complexes; see: a) T. Takahashi, D. Y. Kondakov, N. Suzuki, Organometallics 1994, 13, 3411-3412;
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This excellent stereoselectivity is considerably higher than that reported for related cyclizations based on titanium(II) and zirconium(II)- complexes; see: a) T. Takahashi, D. Y. Kondakov, N. Suzuki, Organometallics 1994, 13, 3411-3412;
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Takayama, Y.1
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0028135651
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Previous ly reported procedures to prepare similar carbocycles afforded lower yields and poorer chemical compatibility; see: a W. Oppolzer, F. Schröder, Tetrahedron Lett. 1994, 35, 7939-7942;
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Previous ly reported procedures to prepare similar carbocycles afforded lower yields and poorer chemical compatibility; see: a) W. Oppolzer, F. Schröder, Tetrahedron Lett. 1994, 35, 7939-7942;
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44
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34547464719
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33845279655
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3SnH-induced radical cyclization of an allylic bromide closely related to carbonate 1 provided considerably worse regio- (91:9 5-exo/6-endo) and stereoselectivity (cis/trans, 65:35) than those afforded by the Ni/Ti system; see: G. Stork, M. E. Reynolds, J. Am. Chem. Soc. 1988, 110, 6911-6913.
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3SnH-induced radical cyclization of an allylic bromide closely related to carbonate 1 provided considerably worse regio- (91:9 5-exo/6-endo) and stereoselectivity (cis/trans, 65:35) than those afforded by the Ni/Ti system; see: G. Stork, M. E. Reynolds, J. Am. Chem. Soc. 1988, 110, 6911-6913.
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