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33646438242
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Though technically a dienone, one of the dienone olefins in the scaffold is not in conjugation with the carbonyl, rendering it unreactive as a conjugate acceptor (vide infra),
-
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17
-
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33646437928
-
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note
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15 confirmed that conjugate addition occurs diastereoselectively from the convex face of the enone.
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18
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0033958525
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19
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33646463606
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Institute for Chemistry and Cell Biology, Harvard University, Cambridge. MA
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Institute for Chemistry and Cell Biology, Harvard University, Cambridge. MA.
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20
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0035961490
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The standard resin used by the ICCB is a derivative of 500 μm polystyrene resin with a diisopropyl-p-methoxyphenylsilyl terminus. See: (a) Sternson, S. M.; Louca, J. B.; Wong, J. C.; Schreiber, S. L. J. Am. Chem. Soc. 2001, 123, 1740-1747.
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23
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33646463014
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See ref 19
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See ref 19.
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24
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For an analysis of site-site interactions, see: Hodge, P. Chem. Soc. Rev. 1997, 26, 417-424.
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33646463165
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note
-
1H NMR of product 16, which was cleaved from the resin with HF·pyridine.
-
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-
-
32
-
-
33646458846
-
-
note
-
1H NMR and mass recovery of 16, obtained by HF-pyridine-mediated cleavage of 18a and 18b from the resin. All subsequent studies showed that the mixture of 18a and 18b behaved as if it were one isomer. Furthermore, the distinction between 18a and 18b is transient. Following cleavage from the resin, both 18a and 18b yield the same product (16).
-
-
-
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34
-
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33646442345
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See ref 24
-
(b) See ref 24.
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36
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33747176412
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33646451347
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note
-
L-selectride, K-selectride. LAH, DIBAL-H, 9-BBN, and BH, each led to a complex mixture of products including products of over-reduction and allyl group cleavage.
-
-
-
-
40
-
-
33646438695
-
-
note
-
A mixture of oxime geometrical isomers was generally observed, in most cases with a ratio >4:1, presumably in favor of the E isomer where the oxime substituent is oriented away from the carpanone core.
-
-
-
-
41
-
-
33646462314
-
-
note
-
1H NMR spectra for all numbered compounds produced in the solid phase are included in the Supporting Information.
-
-
-
-
43
-
-
33646458696
-
-
note
-
Depending on the thiol, the outcomes included no reaction, 1,4-thiol incorporation only, oxime formation only, and the desired MCR. The results could not be correlated with the structure of the thiol.
-
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44
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0000096835
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47
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11844255741
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For recent insights into the mechanism of this copper-mediated reaction, see: Himo, F.; Lovell, T.; Hilgraf, R.; Rostovtsev, V. V.; Noodleman, L.; Sharpless, K. B.; Fokin, V. V. J. Am. Chem. Soc. 2005, 127, 210-216.
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48
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33646456485
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note
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We speculate that the increased coordinating capability of highly nitrogenated triazoles and ureas might deliver palladium to the allyl group nearest these functional groups, thus promoting undesired cleavage of the ketal allyl group.
-
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49
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0000456170
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Oxidative coupling of phenols and phenol ethers
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Trost, B. M., Fleming, I., Pattenden, G., Eds.; Pergamon: Oxford
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33646453784
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note
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Due to the statistical improbability ot splitting any mixture of solid-phase resin beads into identical heterogeneous batches, a certain percentage of the theoretical number of compounds in any split-and-pool library will not be made. This percentage is minimised when multiple copies of the library are prepared. Three copies of the carpanone library were prepared.
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55
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33646465294
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note
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This process is known as position encoding.
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