Copper-catalyzed enantioselective propargylic amination of propargylic esters with amines: Copper-allenylidene complexes as key intermediates

Journal of the American Chemical Society

Volumn 132, Issue 30, 2010, Pages 10592-10608

  Hattori, Gaku ^a   Sakata, Ken ^b   Matsuzawa, Hiroshi ^a   Tanabe, Yoshiaki ^a   Miyake, Yoshihiro ^a   Nishibayashi, Yoshiaki ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b HOSHI UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALLENYLIDENE COMPLEXES; CARBON ATOMS; CATALYTIC REACTIONS; CHIRAL LIGAND; DENSITY FUNCTIONAL THEORY CALCULATIONS; DIPHOSPHINES; DIRECT METHOD; ENANTIOSELECTIVE; HIGH ENANTIOSELECTIVITY; IN-SITU; MODEL REACTIONS; OPTICALLY ACTIVE; PROPARGYLIC AMINES; PROPARGYLIC ESTER; RATE DETERMINING STEP; REACTION PATHWAYS; RELATIVE RATE CONSTANTS; SECONDARY AMINES;

AMINATION; AMINES; CATALYSIS; COPPER; DENSITY FUNCTIONAL THEORY; ENANTIOSELECTIVITY; ESTERIFICATION; ESTERS; RATE CONSTANTS; REACTION INTERMEDIATES;

COPPER COMPOUNDS;

ACETIC ACID; AMINE; ANILINE DERIVATIVE; CARBON; COPPER COMPLEX; ESTER DERIVATIVE; LIGAND; NUCLEOPHILE; PHOSPHINE DERIVATIVE;

AMINATION; ARTICLE; ATOM; CATALYSIS; CHEMICAL REACTION; CHIRALITY; DENSITY FUNCTIONAL THEORY; ELECTROPHILICITY; ENANTIOSELECTIVITY; MOLECULAR MODEL; STEREOCHEMISTRY; STOICHIOMETRY;

ALKYNES; AMINATION; AMINES; CATALYSIS; COPPER; ESTERS; STEREOISOMERISM;

EID: 77955025634     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja1047494     Document Type: Article

References (152)

1. For selected reviews, see: Tsuji, J. Palladium Reagents and Catalysts; Wiley: New York, 1995; p 290.
2. Trost, B. M. and Van Vranken, D. L. Chem. Rev. 1996, 96, 395
3. Trost, B. M. and Lee, C. B. In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I., Ed.; Wiley-VCH: New York, 2000; p 593.
4. Trost, B. M. and Crawley, M. L. Chem. Rev. 2003, 103, 2921
5. Nishibayashi, Y. and Uemura, S. In Comprehensive Organometallic Chemistry III; Crabtree, R. H. and Mingos, D. M. P., Eds.; Elsevier: Amsterdam, 2007; Vol. 11, p 75.
6. Lu, Z. and Ma, S. Angew. Chem., Int. Ed. 2008, 47, 258
7. Brandsma, L. Preparative Acetylene Chemistry, 2nd ed.; Elsevier: Amsterdam, 1988.
8. Modern Acetylene Chemistry; Stang, P. J. and Diederich, F., Eds.; VCH: Weinheim, 1995.
9. Acetylene Chemistry; Diederich, F., Stang, P. J., and Tykwinski, R. R., Eds.; VCH: Weinheim, 2005.
10. Brandsma, L. Synthesis of Acetylenes, Allenes and Cumulenes: Methods and Techniques; Elsevier: Amsterdam, 2004.
11. For recent reviews, see: Tejedor, D., López-Tosco, S., Cruz-Acosta, F., Méndez-Abt, G., and García-Tellado, F. Angew. Chem., Int. Ed. 2009, 48, 2090
12. Anaya de Parrodi, C. and Walsh, P. J. Angew. Chem., Int. Ed. 2009, 48, 4679
13. For recent reviews, see: Nicholas, K. M. Acc. Chem. Res. 1987, 20, 207
14. Caffyn, A. J. M. and Nicholas, K. M. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., and Wilkinson, G., Eds.; Pergamon: Oxford, 1995; Vol. 12, p 685.
15. Green, J. R. Curr. Org. Chem. 2001, 5, 809
16. Müller, T. J. J. Eur. J. Org. Chem. 2001, 2021
17. Díaz, D. D., Betancort, J. M., and Martín, V. S. Synlett 2007, 343
18. Asymmetric versions of the Nicholas reaction have already been reported: Nicholas, K. M., Mulvaney, M., and Bayer, M. J. Am. Chem. Soc. 1980, 102, 2508
19. Ljungdahl, N., Pera, N. P., Andersson, K. H. O., and Kann, N. Synlett 2008, 394
20. Nishibayashi, Y., Wakiji, I., and Hidai, M. J. Am. Chem. Soc. 2000, 122, 11019
21. Nishibayashi, Y., Wakiji, I., Ishii, Y., Uemura, S., and Hidai, M. J. Am. Chem. Soc. 2001, 123, 3393
22. Nishibayashi, Y., Inada, Y., Hidai, M., and Uemura, S. J. Am. Chem. Soc. 2002, 124, 7900
23. Nishibayashi, Y., Yoshikawa, M., Inada, Y., Hidai, M., and Uemura, S. J. Am. Chem. Soc. 2002, 124, 11846
24. Inada, Y., Nishibayashi, Y., Hidai, M., and Uemura, S. J. Am. Chem. Soc. 2002, 124, 15172
25. Nishibayashi, Y., Inada, Y., Yoshikawa, M., Hidai, M., and Uemura, S. Angew. Chem., Int. Ed. 2003, 42, 1495
26. Nishibayashi, Y., Inada, Y., Hidai, M., and Uemura, S. J. Am. Chem. Soc. 2003, 125, 6060
27. Nishibayashi, Y., Yoshikawa, M., Inada, Y., Hidai, M., and Uemura, S. J. Org. Chem. 2004, 69, 3408
28. Nishibayashi, Y., Milton, M. D., Inada, Y., Yoshikawa, M., Wakiji, I., Hidai, M., and Uemura, S. Chem.=Eur. J. 2005, 11, 1433
29. Inada, Y., Yoshikawa, M., Milton, M. D., Nishibayashi, Y., and Uemura, S. Eur. J. Org. Chem. 2006, 881
30. Nishibayashi, Y., Shinoda, A., Miyake, Y., Matsuzawa, H., and Sato, M. Angew. Chem., Int. Ed. 2006, 45, 4835
31. Daini, M., Yoshikawa, M., Inada, Y., Uemura, S., Sakata, K., Kanao, K., Miyake, Y., and Nishibayashi, Y. Organometallics 2008, 27, 2046
32. Yamauchi, Y., Miyake, Y., and Nishibayashi, Y. Organometallics 2009, 28, 48
33. Kanao, K., Miyake, Y., and Nishibayashi, Y. Organometallics 2010, 29, 2126
34. Nishibayashi, Y., Imajima, H., Onodera, G., Hidai, M., and Uemura, S. Organometallics 2004, 23, 26
35. Nishibayashi, Y., Imajima, H., Onodera, G., Inada, Y., Hidai, M., and Uemura, S. Organometallics 2004, 23, 5100
36. Miyake, Y., Endo, S., Nomaguchi, Y., Yuki, M., and Nishibayashi, Y. Organometallics 2008, 27, 4017
37. Miyake, Y., Endo, S., Yuki, M., Tanabe, Y., and Nishibayashi, Y. Organometallics 2008, 27, 6039
38. Tanabe, Y., Kanao, K., Miyake, Y., and Nishibayashi, Y. Organometallics 2009, 28, 1138
39. The result of the density functional theory calculation on the model reaction also supports the proposed reaction pathway of the ruthenium-catalyzed propargylic substitution reactions of propargylic alcohols with nucleophiles, where ruthenium-allenylidene complexes work as key intermediates: Ammal, S. C., Yoshikai, N., Inada, Y., Nishibayashi, Y., and Nakamura, E. J. Am. Chem. Soc. 2005, 127, 9428
40. Sakata, K., Miyake, Y., and Nishibayashi, Y. Chem. Asian J. 2009, 4, 81
41. For recent reviews of transition metal-allenylidene complexes, see: Bruneau, C. and Dixneuf, P. H. Angew. Chem., Int. Ed. 2006, 45, 2176
42. Metal Vinylidenes and Allenylidenes in Catalysis: From Reactivity to Applications in Synthesis; Bruneau, C. and Dixneuf, P. H., Eds.; Wiley-VCH: Weinheim, 2008.
43. Cadierno, V. and Gimeno, J. Chem. Rev. 2009, 109, 3512
44. Nishibayashi, Y., Yoshikawa, M., Inada, Y., Milton, M. D., Hidai, M., and Uemura, S. Angew. Chem., Int. Ed. 2003, 42, 2681
45. Milton, M. D., Inada, Y., Nishibayashi, Y., and Uemura, S. Chem. Commun. 2004, 2712
46. Milton, M. D., Onodera, G., Nishibayashi, Y., and Uemura, S. Org. Lett. 2004, 6, 3993
47. Nishibayashi, Y., Yoshikawa, M., Inada, Y., Hidai, M., and Uemura, S. J. Am. Chem. Soc. 2004, 126, 16066
48. Onodera, G., Matsumoto, H., Milton, M. D., Nishibayashi, Y., and Uemura, S. Org. Lett. 2005, 7, 4029
49. Onodera, G., Matsumoto, H., Nishibayashi, Y., and Uemura, S. Organometallics 2005, 24, 5799
50. Onodera, G., Nishibayashi, Y., and Uemura, S. Organometallics 2006, 25, 35
51. Yamauchi, Y., Onodera, G., Sakata, K., Yuki, M., Miyake, Y., Uemura, S., and Nishibayashi, Y. J. Am. Chem. Soc. 2007, 129, 5175
52. Yamauchi, Y., Yuki, M., Tanabe, Y., Miyake, Y., Inada, Y., Uemura, S., and Nishibayashi, Y. J. Am. Chem. Soc. 2008, 130, 2908
53. Yada, Y., Miyake, Y., and Nishibayashi, Y. Organometallics 2008, 27, 3614
54. For reviews on catalytic propargylic substitution reactions, see: Nishibayashi, Y. and Uemura, S. Curr. Org. Chem. 2006, 10, 135
55. Nishibayashi, Y. and Uemura, S. In Comprehensive Organometallic Chemistry III; Crabtree, R. H. and Mingos, D. M. P., Eds.; Elsevier: Amsterdam, 2007; Vol. 11, p 123.
56. Kabalka, G. W. and Yao, M.-L. Curr. Org. Synth. 2008, 5, 28
57. Ljungdahl, N. and Kann, N. Angew. Chem., Int. Ed. 2009, 48, 642
58. Miyake, Y., Uemura, S., and Nishibayashi, Y. ChemCatChem 2009, 1, 342
59. Detz, R. J., Hiemstra, H., and van Maarseveen, J. H. Eur. J. Org. Chem. 2009, 6263
60. Nishibayashi, Y., Onodera, G., Inada, Y., Hidai, M., and Uemura, S. Organometallics 2003, 22, 873
61. Inada, Y., Nishibayashi, Y., and Uemura, S. Angew. Chem., Int. Ed. 2005, 44, 7715
62. Matsuzawa, H., Miyake, Y., and Nishibayashi, Y. Angew. Chem., Int. Ed. 2007, 46, 6488
63. Matsuzawa, H., Kanao, K., Miyake, Y., and Nishibayashi, Y. Org. Lett. 2007, 9, 5561
64. Kanao, K., Matsuzawa, H., Miyake, Y., and Nishibayashi, Y. Synthesis 2008, 3869
65. Kanao, K., Miyake, Y., and Nishibayashi, Y. Organometallics 2009, 28, 2920
66. For a recent review, see: Catalytic Asymmetric Friedel-Crafts Alkylations; Bandini, M. and Umani-Ronchi, A., Eds.; VCH: Weinheim, 2009.
67. Fukamizu, K., Miyake, Y., and Nishibayashi, Y. J. Am. Chem. Soc. 2008, 130, 10498
68. Smith, S. W. and Fu, G. C. J. Am. Chem. Soc. 2008, 130, 12645
69. Imada, Y., Yuasa, M., Nakamura, I., and Murahashi, S.-I. J. Org. Chem. 1994, 59, 2282
70. Geri, R., Polizzi, C., Lardicci, L., and Caporusso, A. M. Gazz. Chim. Ital. 1994, 124, 241
71. Godfrey, J. D., Jr., Mueller, R. H., Sedergran, T. C., Soundararajan, N., and Colandrea, V. J. Tetrahedron Lett. 1994, 35, 6405
72. Detz, R. J., Delville, M. M. E., Hiemstra, H., and van Maarseveen, J. H. Angew. Chem., Int. Ed. 2008, 47, 3777 Prof. van Maarseveen and co-workers achieved the first enantioselective propargylic amination and presented a part of their result at the PAC Symposium 2007 (March 1, 2007, Utrecht).
73. A preliminary result of the copper-catalyzed enantioselective propargylic amination has already been reported by our group: Hattori, G., Matsuzawa, H., Miyake, Y., and Nishibayashi, Y. Angew. Chem., Int. Ed. 2008, 47, 3781
74. (R)-BINAP = (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl: Noyori, R. and Takaya, H. Acc. Chem. Res. 1990, 23, 345
75. BIPHEP = 2,2′-bis(diphenylphosphino)-1,1′-biphenyl: Schmid, R., Foricher, J., Cereghetti, M., and Schönholzer, P. Helv. Chim. Acta 1991, 74, 370
76. Porco, J. A., Jr., Schoenen, F. J., Stout, T. J., Clardy, J., and Schreiber, S. L. J. Am. Chem. Soc. 1990, 112, 7410
77. Nicolaou, K. C., Hwang, C.-K., Smith, A. L., and Wendeborn, S. V. J. Am. Chem. Soc. 1990, 112, 7416
78. Yu, P. H., Davis, B. A., and Boulton, A. A. J. Med. Chem. 1992, 35, 3705
79. Jiang, B. and Xu, M. Angew. Chem., Int. Ed. 2004, 43, 2543
80. Yamamoto, Y., Hayashi, H., Saigoku, T., and Nishiyama, H. J. Am. Chem. Soc. 2005, 127, 10804
81. Fleming, J. J. and Du Bois, J. J. Am. Chem. Soc. 2006, 128, 3926
82. For a recent review, see Zani, L. and Bolm, C. Chem. Commun. 2006, 4263
83. For examples, see: Wei, C. and Li, C.-J. J. Am. Chem. Soc. 2002, 124, 5638
84. Koradin, C., Polborn, K., and Knochel, P. Angew. Chem., Int. Ed. 2002, 41, 2535
85. Knöpfel, T. F., Aschwanden, P., Ichikawa, T., Watanabe, T., and Carreira, E. M. Angew. Chem., Int. Ed. 2004, 43, 5971
86. Dube, H., Gommermann, N., and Knochel, P. Synthesis 2004, 2015
87. Sakai, N., Uchida, N., and Konakahara, T. Synlett 2008, 1515
88. In related work, we have found the copper-catalyzed diastereo- and enantioselective sequential reactions of propargylic acetates with (E)-2,4-pentadienylaniline to give the corresponding 1,2-disubstituted tetrahydroisoindoles in high yields with high diastereo- and enantioselectivities, where only a single copper salt works as a catalyst to promote both propargylic amination and intramolecular [4+2] cycloaddition reaction: Hattori, G., Miyake, Y., and Nishibayashi, Y. ChemCatChem 2010, 2, 155
89. (S, S)-DIOP = (4 S,5 S)- O -isopropylidene-2,3-dihydroxy-1,4- bis(diphenylphosphino)butane: Kagan, H. B. and Dang, T.-P. J. Am. Chem. Soc. 1972, 94, 6429
90. (R, R)-QuinoxP* = (R, R)-2,3-bis(tert -butylmethylphosphino) quinoxaline: Imamoto, T., Sugita, K., and Yoshida, K. J. Am. Chem. Soc. 2005, 127, 11934
91. Trost ligand = (1 R,2 R)-1,2-diaminocyclohexane- N, N -μ-bis-2′-(diphenylphosphinobenzoyl): Trost, B. M., Machacek, M. R., and Aponick, A. Acc. Chem. Res. 2006, 39, 747 and references therein
92. (R, R)-Me-DUPHOS = 1,2-bis-((2 R,5 R)-2,5-dimethylphospholano)benzene: Burk, M. J. Acc. Chem. Res. 2000, 33, 363 and references therein
93. (S, S)-CHIRAPHOS = (2 S,3 S)-bis(diphenylphosphino)butane: Fryzuk, M. D. and Bosnich, B. J. Am. Chem. Soc. 1977, 99, 6262
94. (R)-MeO-MOP = (R)-2-(diphenylphophino)-2′-methoxy-1,1′- biphenyl: Hayashi, T. Acc. Chem. Res. 2000, 33, 354 and references therein
95. (S)-(S)-ip-FOXAP = (S, S)-[2-(4′-isopropyloxazolin-2′-yl) ferrocenyl]diphenylphosphine: Miyake, Y., Nishibayashi, Y., and Uemura, S. Synlett 2008, 1747 and references therein
96. (S)-(R, R)-Phosphoramidite = (S)-(+)-(3,5-dioxa-4-phospha-cyclohepta[2,1- a;3,4- a ′]dinaphthalen-4-yl)bis[(1 R)-1-phenylethyl]amine: de Vries, A. H. M., Meetsma, A., and Feringa, B. L. Angew. Chem., Int. Ed. Engl. 1996, 35, 2374-2376
97. Feringa, B. L., Pineschi, M., Arnold, L. A., Imbos, R., and de Vries, A. H. M. Angew. Chem., Int. Ed. Engl. 1997, 36, 2620-2623
98. 8-BINAP = (R)-2,2′-bis(diphenylphosphino)-5, 5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl: Zhang, X., Mashima, K., Koyano, K., Sayo, N., Kumobayashi, H., Akutagawa, S., and Takaya, H. Tetrahedron Lett. 1991, 32, 7283
99. (R)-SEGPHOS = (R)-5,5′-bis(diphenylphosphino)-4,4′-bi-1,3- benzodioxole: Nagasaki, I., Matsumura, K., Sayo, N., and Saito, T. Acc. Chem. Res. 2007, 40, 1385 and references therein
100. (R)-DIFLUOROPHOS = (R)-5,5′-bis(diphenylphosphino)-2,2′,2, 2′-tetrafluoro-5,5′-bi-1,3-benzodioxole: Duprat de Paule, S., Ratovelomanana-Vidal, V., Gene^t, J.-P., Champion, N., and Dellis, P. Angew. Chem., Int. Ed. 2004, 43, 320
101. (R)-SYNPHOS = (R)-6,6′-bis(diphenylphosphino)-2,2′,3, 3′-tetrahydro-5,5′-bi-1,4-benzodioxin: Duprat de Paule, S., Jeulin, S., Ratovelomanana-Vidal, V., Gene^t, J.-P., Champion, N., and Dellis, P. Tetrahedron Lett. 2003, 44, 823
102. CTH-(R)-P-PHOS = (R)-2,2′,6,6′-tetramethoxy-4,4′- bis(diphenylphosphino)-3,3′-bipyridine: Pai, C.-C., Lin, C.-W., Lin, C.-C., Chen, C.-C., Chan, A. S. C., and Wong, W. T. J. Am. Chem. Soc. 2000, 122, 11513
103. (R)-MeO-BIPHEP = (R)-6,6′-dimethoxy-2,2′- bis(diphenylphosphino)-1,1′-biphenyl: see ref 21.
104. (R)-Ph-MeO-BIPHEP = (R)-3,3′-diphenyl-6,6′-dimethoxy-2, 2′-bis(diphenylphosphino)-1,1′-biphenyl: Wu, S., He, M., and Zhang, X. Tetrahedron: Asymmetry 2004, 15, 2177
105. (R)-Cl-MeO-BIPHEP = (R)-5,5′-dichloro-6,6′-dimethoxy-2, 2′-bis(diphenylphosphino)-1,1′-biphenyl: Huddleston, R. R., Jang, H.-Y., and Krische, M. J. J. Am. Chem. Soc. 2003, 125, 11488
106. Jang, H.-Y., Hughes, F. W., Gong, H., Zhang, J., Brodbelt, J. S., and Krische, M. J. J. Am. Chem. Soc. 2005, 127, 6174
107. Rhee, J. U. and Krische, M. J. J. Am. Chem. Soc. 2006, 128, 10674
108. Skucas, E., Kong, J. R., and Krische, M. J. J. Am. Chem. Soc. 2007, 129, 7242
109. Reactions of 1a with other anilines such as 4-methylaniline, 4-chloroaniline, and 4-trifluoromethylaniline were investigated under the same reaction conditions to give the corresponding propargylic amines in good yields with only a moderate enantioselectivity (45-55% ee). Unfortunately, no propargylic amination occurred at all when primary alkylamines such as tert -butylamine and 1-adamantylamine were used as nucleophiles
110. Baker, R. T., Calabrese, J. C., and Westcott, S. A. J. Organomet. Chem. 1995, 498, 109
111. Pinto, P., Calhorda, M. J., Félix, V., Avilés, T., and Drew, M. G. B. Monatsh. Chem. 2000, 131, 1253
112. The complex 3b has already been prepared by the Lipshutz group, but the crystallographic structure of 3b has not yet been mentioned: Lipshutz, B. H., Frieman, B., and Birkedal, H. Org. Lett. 2004, 6, 2305
113. Díez, J., Gamasa, M. P., Gimeno, J., Aguirre, A., García-Granda, S., Holubova, J., and Falvello, L. R. Organometallics 1999, 18, 662
114. Mealli, C., Godinho, S. S. M. C., and Calhorda, M. J. Organometallics 2001, 20, 1734
115. -1, R 1 (wR 2) = 0.0762 (0.1419) for 18 587 unique reflections and 1032 parameters. Heavy disorder among acetylides and dichloromethane prohibited sufficient refinement of the structure
116. Knotter, D. M., Spek, A. L., and van Koten, G. J. Chem. Soc., Chem. Commun. 1989, 1738
117. Díez, J., Gamasa, M. P., Gimeno, J., Aguirre, A., and García-Granda, S. Organometallics 1991, 10, 380
118. Baxter, C. W., Higgs, T. C., Bailey, P. J., Parsons, S., McLachlan, F., McPartlin, M., and Tasker, P. A. Chem.=Eur. J. 2006, 12, 6166
119. Bruce, M. I., Zaitseva, N. N., Skelton, B. W., Somers, N., and White, A. H. Inorg. Chim. Acta 2007, 360, 681
120. Asano, Y., Ito, H., Hara, K., and Sawamura, M. Organometallics 2008, 27, 5984
121. Straub, B. F. Chem. Commun. 2007, 3868
122. Meldal, M. and Tornøe, C. W. Chem. Rev. 2008, 108, 2952 and references therein
123. Girard, C. and Kagan, H. B. Angew. Chem., Int. Ed. 1998, 37, 2922 and references therein
124. Gommermann, N., Koradin, C., Polborn, K., and Knochel, P. Angew. Chem., Int. Ed. 2003, 42, 5763
125. Lipshutz, B. H., Noson, K., Chrisman, W., and Lower, A. J. Am. Chem. Soc. 2003, 125, 8779
126. Harutyunyan, S. R., López, F., Browne, W. R., Correa, A., Peña, D., Badorrey, R., Meetsma, A., Minnaard, A. J., and Feringa, B. L. J. Am. Chem. Soc. 2006, 128, 9103
127. No copper-allenylidene complex has yet been isolated until now, but the first example of a silver-allenylidene complex has recently been reported: Asay, M., Donnadieu, B., Schoeller, W. W., and Bertrand, G. Angew. Chem., Int. Ed. 2009, 48, 4796 Recently, the first example of a palladium-allenylidene complex has been reported: Kessler, F., Szesni, N., Põ~hako, K., Weibert, B., and Fischer, H. Organometallics 2009, 28, 348
128. Quite recently, we reported the copper-catalyzed enantioselective ring-opening reactions of ethynyl epoxides with amines, where copper-allenylidene complexes were proposed to work as key intermediates: Hattori, G., Yoshida, A., Miyake, Y., and Nishibayashi, Y. J. Org. Chem. 2009, 74, 7603
129. For reviews, see: Exner, O. In Correlation Analysis in Chemisty; Chapman, N. B. and Shorter, J., Eds.; Plenum Press: New York, 1978; Chapter 10.
130. Hansch, C., Leo, A., and Taft, R. W. Chem. Rev. 1991, 91, 165
131. Lee, C., Yang, W., and Parr, R. G. Phys. Rev. B 1988, 37, 785
132. Becke, A. D. J. Chem. Phys. 1993, 98, 5648
133. Stephens, P. J., Devlin, F. J., Chabalowski, C. F., and Frisch, M. J. J. Phys. Chem. 1994, 98, 11623
134. Frisch, M. J.; et al. Gaussian 03, revision D.02; Gaussian, Inc.: Wallingford, CT, 2004.
135. Dolg, M., Wedig, U., Stoll, H., and Preuss, H. J. Chem. Phys. 1987, 86, 866
136. Hehre, W. J., Radom, L., Schleyer, P. v. R., and Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986.
137. Separately, we carried out theoretical calculations of the propargylic amination in the absence of one methanol molecule. In this case, the propargylic amination is considered to proceed via copper-vinylidene complexes as key intermediates (Path B; see Supporting Information for experimental details). However, the energy barriers of the propargylic amination via copper-vinylidene complexes (Path B) are relatively higher than those via copper-acetylide complexes (Path A). Thus, Path A is more preferred than Path B. Some copper-catalyzed transformations of terminal alkynes are considered to proceed via copper-vinylidene complexes as key intermediates. For example, see: Himo, F., Lovell, T., Hilgraf, R., Rostovtsev, V. V., Noodleman, L., Sharpless, K. B., and Fokin, V. V. J. Am. Chem. Soc. 2005, 127, 210
138. Mayer, I. Chem. Phys. Lett. 1983, 97, 270
139. The X-ray analysis of a major enantioisomer of 2ae indicates that the absolute configuration of 2ae is S. The molecular structure of 2ae was confirmed by X-ray analysis. See Supporting Information for experimental details
140. The result of the calculated model structure of the copper-allenylidene complex D′ with the collinearity of the Cu-C(α)-C(β)-C(γ) bond and the dihedral angle (C(1)(phenyl)-C(γ)-Cu-O(methanol)) of -90° supports the edge-to-face interaction between the two phenyl groups, where one of the ortho C-H bonds of the phenyl group in the allenylidene ligand is tilting toward one of the phenyl groups at the phosphorous atom in BIPHEP. The phenyl ring centroid-centroid separation (6.09 Å) of these neighboring two phenyl groups is within the range of phenyl ring centroid separations observed for the existence of aromatic-aromatic interactions (3.4-6.5 Å). To obtain more exact information, we are investigating isolation of the copper-allenylidene complex
141. For the edge-to-face aromatic interaction, see: Burley, S. K. and Petsko, G. A. Science 1985, 229, 23
142. Burley, S. K. and Petsko, G. A. J. Am. Chem. Soc. 1986, 108, 7995
143. Meyer, E. A., Castellano, R. K., and Diederich, F. Angew. Chem., Int. Ed. 2003, 42, 1210
144. Nishio, M. Tetrahedron 2005, 61, 6923
145. Noyori, R., Yamakawa, M., and Hashiguchi, S. J. Org. Chem. 2001, 66, 7931
146. Quite recently, we found that edge-to-face aromatic interaction between two the phenyl groups in the ruthenium-allenylidene complex plays a critical role for the ruthenium-catalyzed enantioselective propargylic substitution reactions: Kanao, K., Tanabe, Y., Miyake, Y., and Nishibayashi, Y. Organometallics 2010, 29, 2381
147. Ohshima, T., Miyamoto, Y., Ipposhi, J., Nakahara, Y., Utsunomiya, M., and Mashima, K. J. Am. Chem. Soc. 2009, 131, 14317
148. Allen, D. W. and Taylor, B. F. J. Chem. Soc., Dalton Trans. 1982, 51
149. Socol, S. M. and Verkade, J. G. Inorg. Chem. 1984, 23, 3487
150. Andersen, N. G., Parvez, M., and Keay, B. A. Org. Lett. 2000, 2, 2817
151. Suárez, A., Mendez-Rojas, M. A., and Pizzano, A. Organometallics 2002, 21, 4611
152. During the preparation of this manuscript, the copper-catalyzed enantioselective propargylic alkylation of propargylic acetates with enamines was reported by using our reaction system, where Cl-MeO-BIPHEP and BINAP worked as good chiral ligands: Fang, P. and Hou, X.-L. Org. Lett. 2009, 11, 4612