Journal of the American Chemical Society
Communication
a
Table 2. Homocoupling of Substrates C and D with OHIPT Catalysts
b
b
b
cat
sub
time (h)
%conv
%yield
%Z
%side product
2*
2*
3
C
D
C
D
C
D
C
D
2/10/24
2/10/24
2/10/24
2/10/24
2/10/24
2/10/24
2/10/24
2/10/24
87/98/>98
83/91/91
85/96/96
82/94/96
33/93/98
37/74/75
72/97/98
72/88/88
87/98/>98
77/85/85
72/89/89
65/72/72
33/93/98
37/74/75
72/97/98
72/88/88
>98/>98/>98
92/92/91
<2/<2/<2
6/6/6
>98/>98/>98
89/83/81
13/7/7
3
17/22/24
<2/<2/<2
<2/<2/<2
<2/<2/<2
4*
4*
5*
5*
>98/>98/93
c
/97/98
>98/>98/>98
96/97/96
<2/<2/<2
a
b
c
0.01 mmol catalyst (5 mol %) in ∼1.5 mL C6D6, loosely capped vial. Determined by 1H NMR spectroscopy of the reaction mixtures. Z content
not determined.
a
Table 3. Homocoupling of Substrates C and D with OHMT Catalysts
b
b
b
cat
sub
time (h)
%conv
%yield
%Z
%side product
6
6
7
7
8
8
9
9
C
D
C
D
C
D
C
D
2/10/24
2/10/24
2/10/24
2/10/24
2/10/24
2/10/24
2/10/24
2/10/24
86/95/>98
85/96/97
81/91/91
84/89/95
66/80/83
36/36/38
91/97/97
78/78/78
75/89/94
47/52/52
73/84/84
55/59/60
66/80/83
36/36/38
84/90/89
64/64/59
47/41/42
83/80/84
61/58/52
>98/85/75
92/91/91
57/57/57
88/87/87
11/6/6
38/44/45
8/7/7
29/30/35
<2/<2/<2
<2/<2/<2
7/7/8
56/53/51
22/25/27
a
b
1
0.01 mmol catalyst (5 mol %) in ∼1.5 mL C6D6, loosely capped vial. Determined by H NMR spectroscopy of the reaction mixtures.
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OHIPT ligand are the most consistently selective in the set of
substrates that were explored. Mo(OHIPT) catalysts are suitable
when the substrate has a trisubstituted internal double bond.
ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental details for all metal complexes, 1,3-diene
substrates, and homocoupled products; crystal parameters, and
data acquistion parameters. This material is available free of
(3) (a) Dewi, P.; Randl, S.; Blechert, S. Tetrahedron Lett. 2005, 46, 577.
(b) Ferrie, L.; Amans, D.; Reymond, S.; Bellosta, V.; Capdevielle, P.;
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AUTHOR INFORMATION
Corresponding Author
■
(4) Woerlee, E. F. G.; Bosma, R. H. A.; van Eijl, J. M. M.; Mol, J. C.
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Notes
The authors declare no competing financial interest.
Soc. 2009, 131, 3844. (b) Flook, M. M.; Jiang, A. J.; Schrock, R. R.;
ACKNOWLEDGMENTS
■
Muller, P.; Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 7962. (c) Flook,
̈
We are grateful to the National Science Foundation (CHE-
0841187 and CHE-1111133 to R.R.S.) and to the National
Institutes of Health (Grant GM-59426 to R.R.S. and A.H.H.) for
financial support. We thank the National Science Foundation for
departmental X-ray diffraction instrumentation (CHE-
0946721), Michael Takase for assistance with the crystallo-
graphic study, and Alejandro G. Lichtscheidl and Hyangsoo
Jeong for samples of catalysts or catalyst precursors.
M. M.; Gerber, L. C. H.; Debelouchina, G. T.; Schrock, R. R.
Macromolecules 2010, 43, 7515. (d) Jiang, A. J.; Zhao, Y.; Schrock, R. R.;
Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 16630. (e) Marinescu, S. C.;
Schrock, R. R.; Muller, P.; Takase, M. K.; Hoveyda, A. H.
̈
Organometallics 2011, 30, 1780. (f) Meek, S. J.; O’Brien, R. V.;
Llaveria, J.; Schrock, R. R.; Hoveyda, A. H. Nature 2011, 471, 461.
(g) Yu, M.; Wang, C.; Kyle, A. F.; Jakubec, P.; Dixon, D. J.; Schrock, R.
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R. R.; Takase, M. K.; Muller, P.; Hoveyda, A. H. J. Am. Chem. Soc. 2011,
̈
133, 20754. (i) Yu, M.; Ibrahem, I.; Hasegawa, M.; Schrock, R. R.;
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