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JLLeghonD.AEvansCarbonAcyatonwithNMethoxy-Nmethyamides-2 Chem 206 The Rutamycin B Synthesis, H Ng, Ph D. Thesis, Harvard University, 1993 / NMe2 C1-C16 Subunit C17-C37 Subunit Problem is to control C=O reactivity on central D-fragment TESO OMOP 0 ESO Me Ho eCN-H2080% Et The Solution E2,78℃c PMBC Me CH2 MOP C-OMe Evans, Rieger, Jones, Kaldor, JOC, 1990, 55, 6260-6268 tetrahedral intel stable for h The X-206 Synthesis, S. L. Bender, Ph. D. Thesis, Harvard University, 1986 0A0°c 人人人 Evans, Bender, Moms J Am. Chem. Soc. 1988, 110, 2506 H23-05-Weinreb Amides-2 11/5/00 8: 25 PMtetrahedral intermediate stable for hours at 0°C Problem is to control C=O reactivity on central D-fragment 35 21 28 30 F D 29 21 D F 17 28 Evans, Rieger, Jones, Kaldor, JOC, 1990, 55, 6260-6268 C28–C29 C20–C21 29 29 29 The Rutamycin B Synthesis, H. Ng, Ph. D. Thesis, Harvard University, 1993 Evans, Bender, Morris J. Am. Chem. Soc. 1988, 110, 2506. The Solution: Et2O, -78 °C LDA, 0 °C 83% The X-206 Synthesis, S. L. Bender, Ph. D. Thesis, Harvard University, 1986 MOP = 1 A 7 + 16 17 21 C1-C16 Subunit C17-C37 Subunit A B C D E F 1 7 15 21 27 35 A D F 35 27 F D E 12 15 21 27 30 35 7 11 11 1 J. L. Leighton, D. A. Evans Carbon Acylation with N-MethoxyN-methylamides-2 Chem 206 several steps 25 5 1 8 17 12 33 20 HF MeCN-H2O 80% 23 26 32 20 LDA 23 20 26 32 97% 26 20 26 32 80% 32 Me N Li NMe2 Me H Me Me Me OMOP Me O O O O X O Me OBn H Me Me N O NMe2 Me O H Et O H M Me O OH Me OH Me Me Me Et PMBO Me TESO O N Et OMe Me Et PMBO N H NMe2 Me Me O O Me O O H O Me OH O O Me OH Me TESO Me O O O O O O Me OH Me Me Me HO Et Me OH Me OH OH Me Me OH Me Me O OH Me Me OMe Me H Me OH Et O O O O OH OR O Me OR Me Me OR Me Me O H O O Me Me O OO O OH Me Me Me OH Me Me O Me OH OH OH O O Et OH Me H OH Me Me H Me H Li O Me Me H H Me H O Me HO Me OH Me HO Me Et H Me Et PMBO Me O H Me I Me O Me O Me Me O O H H Me Me Me CH2 N Me O O N Me NMe2 MeO OMOP H Me H Me Me Me CH2 O Li O O N Me NMe2 MeN OMOP H Me H Me Me Me CH2 O O O OMOP O H Me Et Me H Me Me NH OBn NMe2 O Et Me H OBn Me O Me C Me Me OMe Me HO Me O Me O O H O H23-05-Weinreb Amides-2 11/5/00 8:25 PM