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This must be seen in the light of the fact that steric hindrance close to a double bond can be a significant obstacle in conventional alkene metathesis: the same pertains to sulfur-containing compounds, which are usually problematic in alkene metathesis, cf. ref, 28b-h
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This must be seen in the light of the fact that steric hindrance close to a double bond can be a significant obstacle in conventional alkene metathesis: the same pertains to sulfur-containing compounds, which are usually problematic in alkene metathesis, cf. ref. [28b-h].
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Such iron catalyzed C-C-bond formations can be performed on a multigram scale without difficulty, provided the nucleophile is added rapidly to the reaction mixture to avoid complications by competing Michael addition/elimination reactions. The Grignard reagent 49 can undergo an uncatalyzed 1,4-additon to enoate 10b followed by elimination of HOTf. This sequence affords the undesired (E)-isomer of 50. which is difficult to separate from (Z)-50 by standard means.
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Such iron catalyzed C-C-bond formations can be performed on a multigram scale without difficulty, provided the nucleophile is added rapidly to the reaction mixture to avoid complications by competing Michael addition/elimination reactions. The Grignard reagent 49 can undergo an uncatalyzed 1,4-additon to enoate 10b followed by elimination of HOTf. This sequence affords the undesired (E)-isomer of 50. which is difficult to separate from (Z)-50 by standard means.
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Smith et al. reported that they failed to cleave the N-PMB group off the corresponding macrocyclic 1,3-diene (as opposed to an enyne in our case) prepared by an entirely different route, cf. ref. [23].
-
Smith et al. reported that they failed to cleave the N-PMB group off the corresponding macrocyclic 1,3-diene (as opposed to an enyne in our case) prepared by an entirely different route, cf. ref. [23].
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-
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163
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0023088224
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D. Blasberger, D. Green, S. Carmely, I. Spector, Y. Kashman, Tetrahedron Lett. 1987, 28, 459-462.
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(1987)
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, vol.28
, pp. 459-462
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Blasberger, D.1
Green, D.2
Carmely, S.3
Spector, I.4
Kashman, Y.5
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164
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0038542691
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For a discussion see
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For a discussion see: A. Fürstner, Synlett 1999, 1523-1533.
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(1999)
Synlett
, pp. 1523-1533
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Fürstner, A.1
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166
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0004150157
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Program for the determination of crystal structures, University of Göttingen Germany
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G. M. Sheldrick, SHELXS-97, Program for the determination of crystal structures, University of Göttingen (Germany) 1997.
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(1997)
SHELXS-97
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Sheldrick, G.M.1
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167
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0004150157
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Program for least-squares refinement of crystal structures. University of Göttingen Germany
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G. M. Sheldrick, SHELXL-97, Program for least-squares refinement of crystal structures. University of Göttingen (Germany), 1997.
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(1997)
SHELXL-97
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Sheldrick, G.M.1
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