Stereoselective Construction of Acyclic Carbon Chains by a One-Pot Coupling Process Based on Alkenyloxazoline-Titanium Complexes

Angewandte Chemie - International Edition

Volumn 43, Issue 4, 2004, Pages 490-492

  Mitsui, Kazuhisa ^a   Sato, Takayuki ^a   Urabe, Hirokazu ^a   Sato, Fumie ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Asymmetric synthesis; C C coupling; Diastereoselectivity; Metallacycles; Oxazolines

Indexed keywords

ORGANOMETALLICS; TITANIUM COMPOUNDS;

ACYCLIC CARBON CHAINS; ON-POT COUPLING PROCESS;

CARBON;

CARBON; OXAZOLINE DERIVATIVE; TITANIUM DERIVATIVE;

ARTICLE; ASYMMETRIC SYNTHESIS; CHEMICAL STRUCTURE; CHIRALITY; COMPLEX FORMATION; DIASTEREOISOMER; REACTION ANALYSIS; STEREOCHEMISTRY; X RAY CRYSTALLOGRAPHY;

EID: 0842285875     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352769     Document Type: Article

References (37)

1. For reviews, see: a) K. A. Lutomski, A. I. Meyers in Asymmetric Synthesis, Vol. 3, Part B (Ed.: J. D. Morrison), Academic, Orlando, 1984, pp. 213-274;
2. b) T. G. Gant, A. I. Meyers, Tetrahedron 1994, 50, 2297-2360;
3. c) A. I. Meyers, J. Heterocycl. Chem. 1998, 35, 991-1002.
4. Aryloxazoline-transition metal complexes have found useful applications; see ref. [1b] and A. R. Pape, K. P. Kaliappan, E. P. Kündig, Chem. Rev. 2000, 100, 2917-2940.
5. The olefin complex could be depicted by a few limiting structures involving 24, but all of these are represented by the general form of the metallacyclopropane shown in Scheme 1.
6. For their preparation, see: M. C. Elliott, E. Kruiswijk, J. Chem. Soc. Perkin Trans 1 1999, 3157-3166.
7. F. Sato, H. Urabe in Titanium and Zirconium in Organic Synthesis (Ed.: I. Marek), Wiley-VCH, Weinheim, 2002, pp. 319-354; F. Sato, S. Okamoto, Adv. Synth. Catal. 2001, 343, 759-784; J. J. Eisch, J. Organomet. Chem. 2001, 617-618, 148-157; F. Sato, H. Urabe, S. Okamoto, Chem. Rev. 2000, 100, 2835-2886; O. G. Kulinkovich, A. de Meijere, Chem. Rev. 2000, 100, 2789-2834.
8. F. Sato, H. Urabe in Titanium and Zirconium in Organic Synthesis (Ed.: I. Marek), Wiley-VCH, Weinheim, 2002, pp. 319-354; F. Sato, S. Okamoto, Adv. Synth. Catal. 2001, 343, 759-784; J. J. Eisch, J. Organomet. Chem. 2001, 617-618, 148-157; F. Sato, H. Urabe, S. Okamoto, Chem. Rev. 2000, 100, 2835-2886; O. G. Kulinkovich, A. de Meijere, Chem. Rev. 2000, 100, 2789-2834.
9. F. Sato, H. Urabe in Titanium and Zirconium in Organic Synthesis (Ed.: I. Marek), Wiley-VCH, Weinheim, 2002, pp. 319-354; F. Sato, S. Okamoto, Adv. Synth. Catal. 2001, 343, 759-784; J. J. Eisch, J. Organomet. Chem. 2001, 617-618, 148-157; F. Sato, H. Urabe, S. Okamoto, Chem. Rev. 2000, 100, 2835-2886; O. G. Kulinkovich, A. de Meijere, Chem. Rev. 2000, 100, 2789-2834.
10. F. Sato, H. Urabe in Titanium and Zirconium in Organic Synthesis (Ed.: I. Marek), Wiley-VCH, Weinheim, 2002, pp. 319-354; F. Sato, S. Okamoto, Adv. Synth. Catal. 2001, 343, 759-784; J. J. Eisch, J. Organomet. Chem. 2001, 617-618, 148-157; F. Sato, H. Urabe, S. Okamoto, Chem. Rev. 2000, 100, 2835-2886; O. G. Kulinkovich, A. de Meijere, Chem. Rev. 2000, 100, 2789-2834.
11. F. Sato, H. Urabe in Titanium and Zirconium in Organic Synthesis (Ed.: I. Marek), Wiley-VCH, Weinheim, 2002, pp. 319-354; F. Sato, S. Okamoto, Adv. Synth. Catal. 2001, 343, 759-784; J. J. Eisch, J. Organomet. Chem. 2001, 617-618, 148-157; F. Sato, H. Urabe, S. Okamoto, Chem. Rev. 2000, 100, 2835-2886; O. G. Kulinkovich, A. de Meijere, Chem. Rev. 2000, 100, 2789-2834.
12. For reviews on olefin complexes of Group 4 metals, see: ref [5]; E. Negishi, T. Takahashi, Acc. Chem. Res. 1994, 27, 124-130; E. Negishi in Comprehensive Organic Synthesis, Vol. 5 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, pp. 1163-1184; and S. L. Buchwald, R. B. Nielsen, Chem. Rev. 1988, 88, 1047-1058.
13. For reviews on olefin complexes of Group 4 metals, see: ref [5]; E. Negishi, T. Takahashi, Acc. Chem. Res. 1994, 27, 124-130; E. Negishi in Comprehensive Organic Synthesis, Vol. 5 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, pp. 1163-1184; and S. L. Buchwald, R. B. Nielsen, Chem. Rev. 1988, 88, 1047-1058.
14. For reviews on olefin complexes of Group 4 metals, see: ref [5]; E. Negishi, T. Takahashi, Acc. Chem. Res. 1994, 27, 124-130; E. Negishi in Comprehensive Organic Synthesis, Vol. 5 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, pp. 1163-1184; and S. L. Buchwald, R. B. Nielsen, Chem. Rev. 1988, 88, 1047-1058.
15. For details, see the Supporting Information.
16. The stereochemistry of the minor isomer has not been determined.
17. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
18. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
19. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
20. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
21. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
22. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
23. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
24. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
25. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
26. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
27. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
28. Multicomponent coupling of the ethylene-Group 4 metal complex, acetylene, and aldehyde (or ketone) was reported: B. H. Lipshutz, M. Segi, Tetrahedron 1995, 51, 4407-4420; C. Copéret, E. Negishi, Z. Xi, T. Takahashi, Tetrahedron Lett. 1994, 35, 695-698; C. Zhao, T. Yu, Z. Xi, Chem. Commun. 2002, 142-143; M. G. Thorn, J. E. Hill, S. A. Waratuke, E. S. Johnson, P. E. Fanwick, I. P. Rothwell, J. Am. Chem. Soc. 1997, 119, 8630-8641. However, in these cases, the notion of diastereoselective synthesis is not applicable. In contrast, (internal olefin)-metal complexes could be used for diastereoselective transformations as described in the text, but their generation and the subsequent reactions appear to be retarded because of the enhanced steric hindrance around the olefin portion. Indeed, few examples of their generation and monoaddition to ketones were reported, and the double addition has not been achieved: D. Enders, M. Kroll, G. Raabe, J. Runsink, Angew. Chem. 1998, 110, 1770-1773; Angew. Chem. Int. Ed. 1998, 37, 1673-1675; J. Scholz, S. Kahlert, H. Görls, Organometallics 1998, 17, 2876-2884; J. Scholz, M. Nolte, C. Krüger, Chem. Ber. 1993, 126, 803-809. See also: B. H. Edwards, R. D. Rogers, D. J. Sikora, J. L. Atwood, M. D. Rausch, J. Am. Chem. Soc. 1983, 105, 416-426; J. M. Davis, R. J. Whitby, A. Jaxa-Chamiec, J. Chem. Soc. Chem. Commun. 1991, 1743-1745; S. Kahlert, H. Görls, J. Scholz, Angew. Chem. 1998, 110, 1958-1962; Angew. Chem. Int. Ed 1998, 37, 1857-1861.
29. CCDC-218515 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
30. For reviews, see: T. K. Sarkar in Science of Synthesis, Vol. 4, Organometallic Compounds of As, Sb, Bi and Si (Ed.: I. Fleming), Georg Thieme, Stuttgart, 2002, pp. 837-925; I. Fleming, A. Barbero, D. Walter, Chem. Rev. 1997, 97, 2063-2192; T. K. Sarkar, Synthesis 1990, 1101-1111.
31. For reviews, see: T. K. Sarkar in Science of Synthesis, Vol. 4, Organometallic Compounds of As, Sb, Bi and Si (Ed.: I. Fleming), Georg Thieme, Stuttgart, 2002, pp. 837-925; I. Fleming, A. Barbero, D. Walter, Chem. Rev. 1997, 97, 2063-2192; T. K. Sarkar, Synthesis 1990, 1101-1111.
32. For reviews, see: T. K. Sarkar in Science of Synthesis, Vol. 4, Organometallic Compounds of As, Sb, Bi and Si (Ed.: I. Fleming), Georg Thieme, Stuttgart, 2002, pp. 837-925; I. Fleming, A. Barbero, D. Walter, Chem. Rev. 1997, 97, 2063-2192; T. K. Sarkar, Synthesis 1990, 1101-1111.
33. When the aryl or silyl substituent of vinyloxazolines i s replaced with an alkyl group, the desired coupling product was not formed. For silicon-assisted stabilization of olefin-titanium alkoxide complexes, see R. Mizojiri, H. Urabe, F. Sato, Tetrahedron Lett. 1999, 40, 2557-2560; R. Mizojiri, H. Urabe, F. Sato, J. Org. Chem. 2000, 65, 6217-6222.
34. When the aryl or silyl substituent of vinyloxazolines i s replaced with an alkyl group, the desired coupling product was not formed. For silicon-assisted stabilization of olefin-titanium alkoxide complexes, see R. Mizojiri, H. Urabe, F. Sato, Tetrahedron Lett. 1999, 40, 2557-2560; R. Mizojiri, H. Urabe, F. Sato, J. Org. Chem. 2000, 65, 6217-6222.
35. The pure Z isomer was prepared by the treatment of the (phenylethynyl)oxazoline with 1 followed by hydrolysis. The generation and utility of the intermediate alkynyloxazoline-titanium alkoxide complex will be reported in due course.
36. The further addition of benzaldehyde to the intermediate titanacyclopentene generated according to entry 4 in Table 2 afforded most likely an 82:13:5 mixture of three, isomeric products in 67% yield, which nearly appears to be the sum of the observations of Tables 1 and 2.
37. N.-Y. Shih, M. Albanese, J. C. Anthes, N. I. Carruthers, C. A. Grice, L. Lin, P. Mangiaracina, G. A. Reichard, J. Schwerdt, V. Seidl, S.-C. Wong, J. J. Piwinski, Bioorg. Med. Chem. Lett. 2002, 12, 141-145.