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For select reviews on Pt and Au catalysis in alkyne activation, see
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77956069695
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See Supporting Information for details
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See Supporting Information for details.
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13
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77956083863
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2. Olefin isomerization occurred to some extent when the enone products were resubjected to the reaction conditions
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2. Olefin isomerization occurred to some extent when the enone products were resubjected to the reaction conditions.
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14
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33751147270
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Mergardt, B., Weber, K., Adiwidjaja, G., and Schaumann, E. Angew. Chem., Int. Ed. Engl. 1991, 30, 1687-1688
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15
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77956092391
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2O-catalyzed silicon migration, but in modest yield and low stereoselectivity. See
-
2O-catalyzed silicon migration, but in modest yield and low stereoselectivity. See
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16
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0041701543
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Sakaguchi, K., Higashino, M., and Ohfune, Y. Tetrahedron 2003, 59, 6647-6658
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Sakaguchi, K.1
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20
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77956074313
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In general, isomerization to thermodynamic equilibrium led to an approximately 2:1 mixture of E and Z enone isomers
-
In general, isomerization to thermodynamic equilibrium led to an approximately 2:1 mixture of E and Z enone isomers.
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-
-
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21
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0003417469
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Eds.; Pergamon: Oxford,; Vol. 8, Chapter 3.12
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Hiyama, T. and Kusumoto, T. In Comprehensive Organic Synthesis; Trost, B. M. and Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 8, Chapter 3.12.
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Comprehensive Organic Synthesis
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Hiyama, T.1
Kusumoto, T.2
Trost, B.M.3
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22
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77956092983
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For a recent discussion, see
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For a recent discussion, see
-
-
-
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25
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77956076587
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Most hydrosilylation studies of internal alkynes have achieved regioselectivities primarily through either steric discrimination or intramolecular delivery of tethered silanes. For catalytic regioselective hydrosilylations of internal alkynes apparently reliant on electronic differentiation, see
-
Most hydrosilylation studies of internal alkynes have achieved regioselectivities primarily through either steric discrimination or intramolecular delivery of tethered silanes. For catalytic regioselective hydrosilylations of internal alkynes apparently reliant on electronic differentiation, see
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26
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Hamze, A., Provot, O., Alami, M., and Brion, J.-D. Org. Lett. 2005, 7, 5625-5628
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29
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77956077501
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Tius has described a rhodium-catalyzed hydrosilylation of ynals to provide similar α-selectivity to our system, but steric differentiation was also highly influential. See
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Tius has described a rhodium-catalyzed hydrosilylation of ynals to provide similar α-selectivity to our system, but steric differentiation was also highly influential. See
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-
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31
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77956090446
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Although geometrical considerations are not applicable, it should be noted that substrates based on terminal alkynes were effective in the silyl migration process but provided complex mixtures in the hydrosilylation process. See Supporting Information for details
-
Although geometrical considerations are not applicable, it should be noted that substrates based on terminal alkynes were effective in the silyl migration process but provided complex mixtures in the hydrosilylation process. See Supporting Information for details.
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32
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77956074140
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For a review of the use of α-substituted enones in cross-coupling reactions, see
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For a review of the use of α-substituted enones in cross-coupling reactions, see
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34
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77956078446
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For select reviews, see
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For select reviews, see
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Metal Catalyzed Cross-Coupling Reactions
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45
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77956069093
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The silylenone products were not effective Hiyama coupling partners, likely due to the complicating electrophilicity of the enone under the fluoride-based conditions
-
The silylenone products were not effective Hiyama coupling partners, likely due to the complicating electrophilicity of the enone under the fluoride-based conditions.
-
-
-
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46
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77956093849
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Water additive was crucial to the success of these transformations, most likely facilitating the formation of a disiloxane intermediate which upon fluoride activation is the active transmetallation species. For a relevant discussion, see
-
Water additive was crucial to the success of these transformations, most likely facilitating the formation of a disiloxane intermediate which upon fluoride activation is the active transmetallation species. For a relevant discussion, see
-
-
-
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47
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1842862944
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Denmark, S. E., Sweis, R. F., and Wehrli, D. J. Am. Chem. Soc. 2004, 126, 4865-4875
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Denmark, S.E.1
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48
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77956081715
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Silylenones can also be converted to α-iodoenones by treatment with ICl; see
-
α-Silylenones can also be converted to α-iodoenones by treatment with ICl; see
-
-
-
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50
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77956082026
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This process is generally stereoconvergent, however, as illustrated in the transformations of both 3 and 10 to 11. In contrast, the use of Hiyama couplings enables efficient access to both isomers of the trisubstituted alkenes
-
This process is generally stereoconvergent, however, as illustrated in the transformations of both 3 and 10 to 11. In contrast, the use of Hiyama couplings enables efficient access to both isomers of the trisubstituted alkenes.
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51
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77956079805
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For a related example of accessing alkenes with geometrical complementarity via alkyne activation processes, see
-
For a related example of accessing alkenes with geometrical complementarity via alkyne activation processes, see
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52
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34347246249
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Tomás, M.5
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