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In a control reaction, a 1:1 mixture of diastereomers of 3c afforded product 4c as a 1:1 mixture of diastereomers.
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55
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79959215055
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note
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See the Supporting Information for complete mechanistic and conformational analyses and NOE measurements.
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56
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79959254957
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note
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X-ray crystal structure analysis was carried out on DMAP salt derivative 6a and acid derivative 7a and 10a. CCDC 808910 (5a), CCDC 809096 (diastereomer of 5a), CCDC 809097 (diastereomer of 5c), CCDC 809098 (6a), CCDC 809099 (7a), CCDC 809100 (8b), and CCDC 809101 (10a) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via.
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79959239808
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note
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A possible mechanism for the partial racemization is provided in the Supporting Information.
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79959278181
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note
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The relative stereochemistry of compound 11 was tentatively assigned based on analogy to compound 12. All efforts to grow suitable crystals of compound 11 have been unsuccessful thus far.
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2, MeCN, MeOH, acetone, and THF (tetrahydrofuran), all of which resulted in sluggish reactions or significant decomposition.
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note
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Attempts to prepare enantioenriched 2d were unsuccessful because of racemization of the allylic ether under the crotylation reaction conditions.
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64
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A structural-similarity search of the framework 13 at ¥90% threshold showed no hits. Structural similarity is measured using the Tanimoto equation and the PubChem. dictionary-based binary fingerprint (http://pubchem.ncbi.nlm. nih.gov/).
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