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The term chirality in the phrase "memory of chirality" originally coined by Fuji (Kawabata, T.; Yahiro, K.; Fuji, K. J. Am. Chem. Soc. 1991, 113, 9694-9696) properly refers to the sense of chirality, or configuration. Chirality is retained in the intermediates whether they racemize or remain enantiopure; the same is obviously true of the products. Perhaps a better term would be "memory of configuration".
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33845229256
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note
-
The chloro substituent in these 1,4-benzodiazepin-2-ones derives from the 2-amino-5-chlorobenzophenone starting material, a commercially available intermediate used in the production of diazepam.
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25
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33845209306
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note
-
One possible explanation for the need for excess base is that alkylation occurs more quickly on a KHMDS/potassium enolate mixed aggregate than it does on homomeric potassium enolates.
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26
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0024841252
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28
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0018636458
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This dihedral angle has the same sign as the C2-C3-N4-C5 dihedral, which has historically (Konowal, A.; Snatzke, G.; Alebic-Kolbah, T.; Kajfez, F.; Rendic, S.; Sunjic, V. Biochem. Pharm. 1979, 28, 3109-3113) been used to designate the sense of conformational chirality of the benzodiazepine ring.
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Konowal, A.1
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Sunjic, V.6
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0026681079
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33845551868
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Seebach, D.; Boes, M.; Naef, R.; Schweizer, W. B. J. Am. Chem. Soc. 1983, 105, 5390-5398.
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36
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0034736318
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Kawabata, T.; Chen, J.; Suzuki, H.; Nagae, Y.; Kinoshita, T.; Chancharunee, S.; Fuji, K. Org. Lett. 2000, 2, 3883-3885.
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37
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20344373648
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Kawabata, T.; Chen, J.; Suzuki, H.; Fuji, K. Synthesis 2005, 1368-1377.
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Kawabata, T.1
Chen, J.2
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Fuji, K.4
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38
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33845204497
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unpublished work
-
Consistent with this analysis, preliminary deprotonation/trapping studies of N-i-Pr-1,4-benzodiazepin-2-one (S)-1d indicate the potassium enolate has a racemization barrier of 18 kcal/mol (258 K). In contrast, the same technique indicates only a 12.5 kcal/mol barrier (173 K) for the potassium enolate derived from N-i-Pr-1,4-benzodiazepine-2,5-dione (S)-3d (P. C.-H. Lam, S. L. MacQuarrie-Hunter, and P. R. Carlier, unpublished work).
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-
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Lam, P.C.-H.1
MacQuarrie-Hunter, S.L.2
Carlier, P.R.3
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