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4 an ortho-metalated ruthenium hydride was isolated in which chelation of the carbonyl group to ruthenium was observed in the position trans to the hydride ligand, see ref 27.
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For details concerning catalytic H/D exchange reactions using 1 see: C. P. Lenges, P. S. White, M. Brookhart, J. Am. Chem. Soc. 1999, 121, 4385-4396.
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46
-
-
0344706694
-
-
note
-
The turnover frequency is 0.7 TO/h and compares well with the results for the reaction in cyclohexane.
-
-
-
-
47
-
-
0345137238
-
-
note
-
8 followed by reversible H/D exchange are faster than productive aryl - alkyl coupling.
-
-
-
-
48
-
-
0344274771
-
-
note
-
Organic products have been isolated by chromatography and characterized by NMR spectroscopy and elemental analysis or HRMS; see Supporting Information.
-
-
-
-
49
-
-
0344274770
-
-
note
-
1H NMR resonances for the methylene groups a to the aryl ring (3a, δ 2.65, 4a, δ 2.83; higher alkylation products, δ 3.11).
-
-
-
-
50
-
-
0345137235
-
-
note
-
The relatively high ratio of higher alkylated products suggests that the second alkylation might occur without prior release of the initially alkylated 2a. Also, the observation of secondary alkylation products in the deactivation process (vide infra) suggests this notion.
-
-
-
-
51
-
-
0345568802
-
-
note
-
Independent synthesis of a rhodium olefin complex with 3,3-dimethyl-1-butene was not successful. In situ NMR studies indicate the formation of such complexes as intermediates.
-
-
-
-
52
-
-
0344706692
-
-
note
-
It is curious to note that the ratio of endo to exo products in this reaction increases as the reaction proceeds with exo-3g being the exclusive addition product in the early stages of catalysis, which suggests that intermediates such as 5 or mixed olefin complexes generated from 1 and norbornene show different reactivity as the presumed bis-norbornene rhodium complex, which is assigned as the resting state during norbornene conversion.
-
-
-
-
53
-
-
0345137236
-
-
note
-
Analogous results are observed by Murai and co-workers using the Ru system in the reaction of 1-hexene (see refs 14-22).
-
-
-
-
54
-
-
0345137234
-
-
note
-
2-); 7.95 (m, 2H, Ar); 7.04-7.18 (m, Ar.). MS/EI: 254.18.
-
-
-
-
55
-
-
0344274768
-
-
note
-
3 protected enolate of acetophenone is commercially available.
-
-
-
-
56
-
-
0345568801
-
-
note
-
(b) A referee has suggested that formation of the silyl enolate might occur through a mechanism involving the addition of a rhodium hydride to the vinyl silane followed by β-silyl elimination and release of ethylene to generate a Rh - silyl complex. Insertion of ketone into the Rh -silyl bond followed by β-elimination would generate the silyl enolate and regenerate the rhodium hydride. While we cannot strictly rule out this mechanism, it is not apparent how a Rh - H species could be generated as the chain carrier in this system.
-
-
-
-
57
-
-
0345137232
-
-
note
-
2); 1.96 (s, 3H, Me); 7.38 (s, 1H, Ar); 7.11 (d, 1H, Ar); 6.92 (d, 1H, Ar). MS/EI: 272.16.
-
-
-
-
58
-
-
0344274766
-
-
note
-
No site selectivity regarding the olefin was observed, which suggests that olefin insertion into a Rh hydride can occur with both regiochemistries under these conditions. This is especially remarkable since the exclusive products observed are based on anti-Markovnikov olefin addition. Olefinhydride insertion might be directed by the carbonyl group with respect to regiochemistry; no direct evidence for this is available.
-
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60
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33847799103
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0344274763
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note
-
Labeling studies have shown that C - H bond activation is only observed in the ortho positions of acetophenone with use of the ruthenium catalyst; the other sites are not activated (see ref 16).
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