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f to the product on silica gel, the loading is reduced to 1.05-1.1 equiv. In all cases, this reduction has no detrimental effect on selectivity or yield of the reaction.
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2442418711
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A control reaction was undertaken to determine the relative propensity of a strained alkene and a Michael acceptor toward carborhodation in the present system. When 1.5 equiv each of norbornene and ethyl acrylate were mixed with 1 equiv of phenylboronic acid under standard reaction conditions, only ethyl cinnamate was obtained, indicating that the arylrhodium species generated in this reaction is highly nucleophilic in character. Increasing the amount of norbornene to 5 equiv did not change the outcome of the reaction.
-
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76
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2442537893
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note
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3P (170°). Although t-Bu-amphos chloride has not been measured, its cone angle is assumed to be similar to that of t-BuaP (185°). See ref 24b.
-
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77
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2442489682
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note
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The more reactive [2.2.1]oxabicyclic alkenes were also tested, as well as norbornene, and did not yield any desired ring-closed products.
-
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78
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2442601152
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note
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The C-H insertion product as well as the minor cyclized product was only observed when fluoride was used as base at high temperatures. Fluoride may promote the oxidative process required for C-H insertion, by stabilizing the Rh(III) state.
-
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79
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2442571801
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note
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Presumably, installation of a functional group at the 4-position, such as a methyl group, would prevent this C-H insertion process and promote formation of the desired cyclized product. This process is under examination.
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