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0042801363
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note
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It is important to quench the reaction mixture by addition of ethyl vinyl ether in order to inactivate the catalyst prior to workup.
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53
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0034674252
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For a pertinent review on how branches on an acyclic compound affect the conformation, see: Hoffmann, R. W. Angew. Chem., Int. Ed. 2000, 39, 2054 and literature cited therein. We have briefly studied if changing the relative configuration between the Me and the OMOM branch of the cyclization precursor from anti to syn has an influence on the stereochemical outcome of RCM but found no appreciable effect. Details will be reported in a forthcoming full paper.
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Hoffmann, R.W.1
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For a previous example of the influence of remote substituents on the stereochemical course of RCM. see: (a) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942.
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56
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0042801362
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note
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We believe that the cyclizations reported herein provide a unique opportunity to reach a better understanding of the transition state of RCM reactions because (i) mechanistically well behaved catalysts are employed, (ii) the substrates have a defined site of initiation (the terminal rather than the trisubstituted alkene), and (iii) the strong stereochemical preferences allow to match the results by molecular modeling. Theoretical investigations along these lines are underway.
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57
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0001645448
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Another explanaton for the different stereoselectivity in RCM of the O-protected substrates (23b-d) as compared to the O-unprotected diene 23a relates to the possible in situ formation of phenolate substituted metathesis catalysts in the latter case. Such compounds are known to be catalytically active (cf: Chang, S.; Jones, L.; Wang, C.; Henling, L. M.; Grubbs, R. H. Organometallics 1998, 17, 3460). We thank the referee for pointing out this possibility which is presently studied in our laboratory.
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Chang, S.1
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58
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0000775011
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Thus far, only macrocyclic (Z)-alkenes can be selectively and predicatably formed by metathesis via a new protocol comprising alkyne metathesis followed by Lindlar reduction, cf.: (a) Fürstner, A.; Seidel, G. Angew. Chem. 1998, 110, 1758; Angew. Chem., Int. Ed. 1998, 37, 1734.
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59
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0038731101
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Thus far, only macrocyclic (Z)-alkenes can be selectively and predicatably formed by metathesis via a new protocol comprising alkyne metathesis followed by Lindlar reduction, cf.: (a) Fürstner, A.; Seidel, G. Angew. Chem. 1998, 110, 1758; Angew. Chem., Int. Ed. 1998, 37, 1734.
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For a discussion, see: Fürstner, A. Synlett 1999, 1523.
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Fürstner, A.1
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