Defining the Conformation of Lewis Acid/Lewis Base Complexes: Crystallographic Evidence for Simultaneous σ and π Donation by a Carbonyl Group to a Divalent Boron Lewis Acid

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 3, 1997, Pages 267-269

  Amendola, Michael C ^a   Stockman, Kenneth E ^a   Hoic, Diego A ^a   Davis, William M ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Boron; Carbonyl complexes; Homogeneous catalysis; Lewis acids

Indexed keywords

EID: 0030896291     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199702671     Document Type: Article

References (55)

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2. b) M. Yamaguchi in Comprehensive Organic Synthesis Vol. 1 (Ed.: B. M. Trost), Pergamon, New York, 1991, Chapter 1.11;
3. c) Selectivities in Lewis Acid Promoted Reactions (Ed.: D. Schinzer), Kluwer, Boston, 1989.
4. Early work: a) S. Hashimoto, N. Komeshima, K. Koga, J. Chem. Soc. Chem. Commun. 1979, 437-438; b) M. Bednarski, S. Danishefsky, J. Am. Chem. Soc. 1983, 105, 3716-3717.
5. Early work: a) S. Hashimoto, N. Komeshima, K. Koga, J. Chem. Soc. Chem. Commun. 1979, 437-438; b) M. Bednarski, S. Danishefsky, J. Am. Chem. Soc. 1983, 105, 3716-3717.
6. Recent reviews: a) K. Ishihara, H. Yamamoto, Advances in Catalytic Processes, JAI, Greenwich, CT, 1995, pp. 29-59; b) L. Deloux, M. Srebnik, Chem. Rev. 1993, 93, 763-784; c) K. Mikami, M. Shimizu, Chem. Rev. 1992, 92, 1021-1050; d) K. Narasaka, Synthesis 1991, 1-11.
7. Recent reviews: a) K. Ishihara, H. Yamamoto, Advances in Catalytic Processes, JAI, Greenwich, CT, 1995, pp. 29-59; b) L. Deloux, M. Srebnik, Chem. Rev. 1993, 93, 763-784; c) K. Mikami, M. Shimizu, Chem. Rev. 1992, 92, 1021-1050; d) K. Narasaka, Synthesis 1991, 1-11.
8. Recent reviews: a) K. Ishihara, H. Yamamoto, Advances in Catalytic Processes, JAI, Greenwich, CT, 1995, pp. 29-59; b) L. Deloux, M. Srebnik, Chem. Rev. 1993, 93, 763-784; c) K. Mikami, M. Shimizu, Chem. Rev. 1992, 92, 1021-1050; d) K. Narasaka, Synthesis 1991, 1-11.
9. Recent reviews: a) K. Ishihara, H. Yamamoto, Advances in Catalytic Processes, JAI, Greenwich, CT, 1995, pp. 29-59; b) L. Deloux, M. Srebnik, Chem. Rev. 1993, 93, 763-784; c) K. Mikami, M. Shimizu, Chem. Rev. 1992, 92, 1021-1050; d) K. Narasaka, Synthesis 1991, 1-11.
10. a) S. Shambayati, S. L. Schreiber in Comprehensive Organic Synthesis Vol. 1 (Ed.: B. M. Trost), Pergamon, New York, 1991, Chapter 1.10;
11. b) S. Shambayati, W. E. Crowe, S. L. Schreiber, Angew. Chem. 1990, 102, 273-290; Angew. Chem. Int. Ed. Engl. 1990, 29, 256-272.
12. b) S. Shambayati, W. E. Crowe, S. L. Schreiber, Angew. Chem. 1990, 102, 273-290; Angew. Chem. Int. Ed. Engl. 1990, 29, 256-272.
13. -1 for aldehyde/Lewis acid complexes: T. J. LePage, K. B. Wiberg, J. Am. Chem. Soc. 1988, 110, 6642-6650.
14. Two-point binding of a substrate to a metal: a) T. R. Kelly, A. Whiting, N. S. Chandrakumar, J. Am. Chem. Soc. 1986, 108, 3510-3512; b) K. Maruoka, M. Sakurai, J. Fujiwara, H. Yamamoto, Tetrahedron Lett. 1986, 27, 4895-4898.
15. Two-point binding of a substrate to a metal: a) T. R. Kelly, A. Whiting, N. S. Chandrakumar, J. Am. Chem. Soc. 1986, 108, 3510-3512; b) K. Maruoka, M. Sakurai, J. Fujiwara, H. Yamamoto, Tetrahedron Lett. 1986, 27, 4895-4898.
16. π-Stacking: a) J. M. Hawkins, S. Loren, J. Am. Chem. Soc. 1991, 113, 7794-7795; J. M. Hawkins, S. Loren, M. Nambu, J. Am. Chem. Soc. 1994, 116, 1657-1660; b) E. J. Corey, Y. Matsumura, Tetrahedron Lett. 1991, 32, 6289-6292. E. J. Corey, T.-P. Loh, J. Am. Chem. Soc. 1991, 113, 8966-8967.
17. π-Stacking: a) J. M. Hawkins, S. Loren, J. Am. Chem. Soc. 1991, 113, 7794-7795; J. M. Hawkins, S. Loren, M. Nambu, J. Am. Chem. Soc. 1994, 116, 1657-1660; b) E. J. Corey, Y. Matsumura, Tetrahedron Lett. 1991, 32, 6289-6292. E. J. Corey, T.-P. Loh, J. Am. Chem. Soc. 1991, 113, 8966-8967.
18. π-Stacking: a) J. M. Hawkins, S. Loren, J. Am. Chem. Soc. 1991, 113, 7794-7795; J. M. Hawkins, S. Loren, M. Nambu, J. Am. Chem. Soc. 1994, 116, 1657-1660; b) E. J. Corey, Y. Matsumura, Tetrahedron Lett. 1991, 32, 6289-6292. E. J. Corey, T.-P. Loh, J. Am. Chem. Soc. 1991, 113, 8966-8967.
19. π-Stacking: a) J. M. Hawkins, S. Loren, J. Am. Chem. Soc. 1991, 113, 7794-7795; J. M. Hawkins, S. Loren, M. Nambu, J. Am. Chem. Soc. 1994, 116, 1657-1660; b) E. J. Corey, Y. Matsumura, Tetrahedron Lett. 1991, 32, 6289-6292. E. J. Corey, T.-P. Loh, J. Am. Chem. Soc. 1991, 113, 8966-8967.
20. References to the activation of a carbonyl group by multidentate Lewis acids: J. Vaugeois, M. Simard, J. D. Wuest, Coord. Chem. Rev. 1995, 145, 55-73, and references therein.
21. 1-bound carbonyl group, deactivates the substrate toward nucleophilic addition. For examples and leading references, see: a) P. V. Bonnesen, C. L. Puckett, R. V. Honeychuck, W. H. Hersh, J. Am. Chem. Soc. 1989, 111, 6070-6081; b) N. Quiros Mendez, J. W. Seyler, A. M. Arif, J. A. Gladysz, J. Am. Chem. Soc. 1993, 115, 2323-2334.
22. 1-bound carbonyl group, deactivates the substrate toward nucleophilic addition. For examples and leading references, see: a) P. V. Bonnesen, C. L. Puckett, R. V. Honeychuck, W. H. Hersh, J. Am. Chem. Soc. 1989, 111, 6070-6081; b) N. Quiros Mendez, J. W. Seyler, A. M. Arif, J. A. Gladysz, J. Am. Chem. Soc. 1993, 115, 2323-2334.
23. Structure Correlation Vols. 1 and 2 (Eds.: H.-B. Burgi, J. D. Dunitz), VCH, New York, 1994.
24. R. Boese, N. Finke, T. Keil, P. Paetzold, G. Schmid, Z. Naturforsch. B 1985, 40, 1327-1332.
25. Evidence for effective π donation from a boron-bound substituent to the borabenzene ring: a) G. E. Herberich, B. Schmidt, U. Englert, T. Wagner, Organometallics 1993, 12, 2891-2893; b) A. J. Ashe III, J. W. Kampf, C. Muller, M. Schneider, Organometallics 1996, 15, 387-393, and references therein.
26. Evidence for effective π donation from a boron-bound substituent to the borabenzene ring: a) G. E. Herberich, B. Schmidt, U. Englert, T. Wagner, Organometallics 1993, 12, 2891-2893; b) A. J. Ashe III, J. W. Kampf, C. Muller, M. Schneider, Organometallics 1996, 15, 387-393, and references therein.
27. 3 fragment serves as a powerful electron-withdrawing substituent, comparable to a nitro group: a) B. Nicholls, M. C. Whiting, J. Chem. Soc. 1959, 551-556; b) S. G. Davies, S. J. Coote, C. L. Goodfellow, Advances in Metal-Organic Chemistry Vol. 2, JAI, Greenwich, CT, 1991, pp. 1-57; c) M. F. Semmelhack in Comprehensive Organic Synthesis Vol. 4, (Ed.: B. M. Trost), Pergamon, New York, 1991, Chapter 2.4.
28. 3 fragment serves as a powerful electron-withdrawing substituent, comparable to a nitro group: a) B. Nicholls, M. C. Whiting, J. Chem. Soc. 1959, 551-556; b) S. G. Davies, S. J. Coote, C. L. Goodfellow, Advances in Metal-Organic Chemistry Vol. 2, JAI, Greenwich, CT, 1991, pp. 1-57; c) M. F. Semmelhack in Comprehensive Organic Synthesis Vol. 4, (Ed.: B. M. Trost), Pergamon, New York, 1991, Chapter 2.4.
29. 3 fragment serves as a powerful electron-withdrawing substituent, comparable to a nitro group: a) B. Nicholls, M. C. Whiting, J. Chem. Soc. 1959, 551-556; b) S. G. Davies, S. J. Coote, C. L. Goodfellow, Advances in Metal-Organic Chemistry Vol. 2, JAI, Greenwich, CT, 1991, pp. 1-57; c) M. F. Semmelhack in Comprehensive Organic Synthesis Vol. 4, (Ed.: B. M. Trost), Pergamon, New York, 1991, Chapter 2.4.
30. D. A. Hoic, J. R. Wolf, W. M. Davis, G. C. Fu, Organometallics 1996, 15, 1315-1318.
31. The mechanism of this reaction is under investigation.
32. -3. All non-hydrogen atoms were refined anisotropically; hydrogens were assigned to calculated positions and refined with an overall isotropic thermal parameter. All calculations were perfomed using the TEXSAN crystallographic software package from Molecular Structure Corporation. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-179-132. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: Int. code +(1223)336-033: e-mail: deposit@chemcrys.cam.ac.uk).
33. A complete search of the Cambridge Structural Database provided the following relevant references: a) J. W. Lott, D. F. Gaines, H. Shenhav, R. Schaeffer, J. Am. Chem. Soc. 1973, 95, 3042-3043; b) J. W. Lott, D. F. Gaines, Inorg. Chem. 1974, 13, 2261-2267; c) L. Borodinsky, E. Sinn, R. N. Grimes, ibid. 1982, 21, 1928-1936; d) Z.-T. Wang, E. Sinn, R. N. Grimes, ibid. 1985, 24, 834-839; e) H. Michel, D. Steiner, S. Wocadlo, J. Allwohn, N. Stamatis, W. Massa, A. Berndt, Angew. Chem. 1992, 104, 629-632; Angew. Chem. Int. Ed. Engl. 1992, 31, 607-610; f) D. F. Mullica, E. L. Sappenfield, F. G. A. Stone, S. F. Woollam, Organometallics 1994, 13, 157-166.
34. A complete search of the Cambridge Structural Database provided the following relevant references: a) J. W. Lott, D. F. Gaines, H. Shenhav, R. Schaeffer, J. Am. Chem. Soc. 1973, 95, 3042-3043; b) J. W. Lott, D. F. Gaines, Inorg. Chem. 1974, 13, 2261-2267; c) L. Borodinsky, E. Sinn, R. N. Grimes, ibid. 1982, 21, 1928-1936; d) Z.-T. Wang, E. Sinn, R. N. Grimes, ibid. 1985, 24, 834-839; e) H. Michel, D. Steiner, S. Wocadlo, J. Allwohn, N. Stamatis, W. Massa, A. Berndt, Angew. Chem. 1992, 104, 629-632; Angew. Chem. Int. Ed. Engl. 1992, 31, 607-610; f) D. F. Mullica, E. L. Sappenfield, F. G. A. Stone, S. F. Woollam, Organometallics 1994, 13, 157-166.
35. A complete search of the Cambridge Structural Database provided the following relevant references: a) J. W. Lott, D. F. Gaines, H. Shenhav, R. Schaeffer, J. Am. Chem. Soc. 1973, 95, 3042-3043; b) J. W. Lott, D. F. Gaines, Inorg. Chem. 1974, 13, 2261-2267; c) L. Borodinsky, E. Sinn, R. N. Grimes, ibid. 1982, 21, 1928-1936; d) Z.-T. Wang, E. Sinn, R. N. Grimes, ibid. 1985, 24, 834-839; e) H. Michel, D. Steiner, S. Wocadlo, J. Allwohn, N. Stamatis, W. Massa, A. Berndt, Angew. Chem. 1992, 104, 629-632; Angew. Chem. Int. Ed. Engl. 1992, 31, 607-610; f) D. F. Mullica, E. L. Sappenfield, F. G. A. Stone, S. F. Woollam, Organometallics 1994, 13, 157-166.
36. A complete search of the Cambridge Structural Database provided the following relevant references: a) J. W. Lott, D. F. Gaines, H. Shenhav, R. Schaeffer, J. Am. Chem. Soc. 1973, 95, 3042-3043; b) J. W. Lott, D. F. Gaines, Inorg. Chem. 1974, 13, 2261-2267; c) L. Borodinsky, E. Sinn, R. N. Grimes, ibid. 1982, 21, 1928-1936; d) Z.-T. Wang, E. Sinn, R. N. Grimes, ibid. 1985, 24, 834-839; e) H. Michel, D. Steiner, S. Wocadlo, J. Allwohn, N. Stamatis, W. Massa, A. Berndt, Angew. Chem. 1992, 104, 629-632; Angew. Chem. Int. Ed. Engl. 1992, 31, 607-610; f) D. F. Mullica, E. L. Sappenfield, F. G. A. Stone, S. F. Woollam, Organometallics 1994, 13, 157-166.
37. A complete search of the Cambridge Structural Database provided the following relevant references: a) J. W. Lott, D. F. Gaines, H. Shenhav, R. Schaeffer, J. Am. Chem. Soc. 1973, 95, 3042-3043; b) J. W. Lott, D. F. Gaines, Inorg. Chem. 1974, 13, 2261-2267; c) L. Borodinsky, E. Sinn, R. N. Grimes, ibid. 1982, 21, 1928-1936; d) Z.-T. Wang, E. Sinn, R. N. Grimes, ibid. 1985, 24, 834-839; e) H. Michel, D. Steiner, S. Wocadlo, J. Allwohn, N. Stamatis, W. Massa, A. Berndt, Angew. Chem. 1992, 104, 629-632; Angew. Chem. Int. Ed. Engl. 1992, 31, 607-610; f) D. F. Mullica, E. L. Sappenfield, F. G. A. Stone, S. F. Woollam, Organometallics 1994, 13, 157-166.
38. A complete search of the Cambridge Structural Database provided the following relevant references: a) J. W. Lott, D. F. Gaines, H. Shenhav, R. Schaeffer, J. Am. Chem. Soc. 1973, 95, 3042-3043; b) J. W. Lott, D. F. Gaines, Inorg. Chem. 1974, 13, 2261-2267; c) L. Borodinsky, E. Sinn, R. N. Grimes, ibid. 1982, 21, 1928-1936; d) Z.-T. Wang, E. Sinn, R. N. Grimes, ibid. 1985, 24, 834-839; e) H. Michel, D. Steiner, S. Wocadlo, J. Allwohn, N. Stamatis, W. Massa, A. Berndt, Angew. Chem. 1992, 104, 629-632; Angew. Chem. Int. Ed. Engl. 1992, 31, 607-610; f) D. F. Mullica, E. L. Sappenfield, F. G. A. Stone, S. F. Woollam, Organometallics 1994, 13, 157-166.
39. A complete search of the Cambridge Structural Database provided the following relevant references: a) J. W. Lott, D. F. Gaines, H. Shenhav, R. Schaeffer, J. Am. Chem. Soc. 1973, 95, 3042-3043; b) J. W. Lott, D. F. Gaines, Inorg. Chem. 1974, 13, 2261-2267; c) L. Borodinsky, E. Sinn, R. N. Grimes, ibid. 1982, 21, 1928-1936; d) Z.-T. Wang, E. Sinn, R. N. Grimes, ibid. 1985, 24, 834-839; e) H. Michel, D. Steiner, S. Wocadlo, J. Allwohn, N. Stamatis, W. Massa, A. Berndt, Angew. Chem. 1992, 104, 629-632; Angew. Chem. Int. Ed. Engl. 1992, 31, 607-610; f) D. F. Mullica, E. L. Sappenfield, F. G. A. Stone, S. F. Woollam, Organometallics 1994, 13, 157-166.
40. The shortness of the B-O bond could also reflect the high Lewis acidity of the σ-symmetry orbital on boron.
41. Preliminary data indicate that the conversion of 2 to 3 proceeds through an addition-elimination mechanism.
42. -3. All non-hydrogen atoms were refined anisotropically; hydrogens were assigned to calculated positions and refined with an overall isotropic thermal parameter. The Siemens Software Package (SMART, SAINT, XPREP, SHELXTL) was used on a Silicon Graphics INDY workstation to handle all calculations.
43. 3] complexes of other carbonyl compounds.
44. NOE experiments on 3 suggest that in solution, as in the solid state, the Lewis acid binds syn to the hydrogen of the aldehyde.
45. Complexes of carbonyl groups with certain cationic Lewis acids that bear a vacant p orbital have been predicted to adopt linear geometries: D. J. Nelson, J. Org. Chem. 1986, 51, 3185-3186, and references therein.
46. 2-hybridized, and the oxygen 2p orbital is properly oriented for interaction with the borabenzene it system. The details of this X-ray crystallographic study will be published elsewhere.
47. 3 adduct: a) benzaldehyde: M. T. Reetz, M. Hullmann, W. Massa, S. Berger, P. Rademacher, P. Heymanns, J. Am. Chem. Soc. 1986, 108, 2405-2408; b) 2-methylacrolein: E. J. Corey, T.-P. Loh, S. Sarshar, M. Azimioara, Tetrahedron Lett. 1992, 33, 6945-6948.
48. 3 adduct: a) benzaldehyde: M. T. Reetz, M. Hullmann, W. Massa, S. Berger, P. Rademacher, P. Heymanns, J. Am. Chem. Soc. 1986, 108, 2405-2408; b) 2-methylacrolein: E. J. Corey, T.-P. Loh, S. Sarshar, M. Azimioara, Tetrahedron Lett. 1992, 33, 6945-6948.
49. a) Methyl crotonate: ref. [7a]: b) 1,1,3,3-tetramethylurea: S. Neyses, P. Paetzold, U. Englert, Struct. Chem. 1994, 5, 51.
50. X-ray diffraction studies of free 3-aminoacroleins: a) S. Kulpe, B. Schulz, Krist. Tech. 1979, 14, 159; b) C. Bai, Z. Yu, H. Fu, Y. Tang, Jiegou Huaxue 1984, 3, 65 (Cambridge Structural Database CIHZOI).
51. X-ray diffraction studies of free 3-aminoacroleins: a) S. Kulpe, B. Schulz, Krist. Tech. 1979, 14, 159; b) C. Bai, Z. Yu, H. Fu, Y. Tang, Jiegou Huaxue 1984, 3, 65 (Cambridge Structural Database CIHZOI).
52. The spectra were assigned by combined NOE and HMQC experiments. See: A. Bax. S. Subramanian, J. Magn. Reson. 1986, 67, 565-569.
53. 1H chemical shifts of the hydrogens attached to these carbons. See: R. F. Childs, D. L. Mulholland, A. Nixon, Can. J. Chem. 1982, 60, 801-808.
54. Our initial attempts to determine by NMR the barrier for rotation about the B-O bond have been unsuccessful.
55. Computational studies of borabenzene-aldehyde complexes are underway (Prof. M. DiMare, University of California, Santa Barbara, unpublished results).