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Volumn 21, Issue 23, 2015, Pages 8403-8407

Directed hydrogenations and an Ireland-Claisen rearrangement linked to Evans-Tishchenko chemistry: The highly efficient total synthesis of the marine cyclodepsipeptide doliculide

Author keywords

actin; Claisen rearrangement; doliculide; hydrogenation; total synthesis

Indexed keywords

CHEMICAL BONDS; CHEMICAL REACTIONS; CONDENSATION REACTIONS; KETONES; PROTEINS; SYNTHESIS (CHEMICAL);

EID: 84930197692     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201501252     Document Type: Article
Times cited : (14)

References (43)
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    • Pfaltz and co-workers have recently presented a strategy for the convergent synthesis of long-chain polydeoxypropionates that employs the stereoselective catalytic hydrogenation of trisubstituted internal double bonds as key steps:, M. C. Pischl, C. F. Weise, S. Haseloff, M.-A. Müller, A. Pfaltz, C. Schneider, Chem. Eur. J. 2014, 20, 17360-17374.
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    • The absolute configuration of the newly formed hydroxyl-bearing stereocenter in 17 was confirmed by conversion into the corresponding acetonide 18 (after debenzylation) and analysis of its 13C NMR spectrum. The 13C chemical shifts of the two ketal methyl groups in 18 were observed at δ=24.34 and 24.41 ppm, whereas the quaternary ketal carbon appeared at 100.8 ppm. These data are in excellent agreement with the predicted shifts for acetonides of anti-1,3-diols:, S. D. Rychnovsky, B. N. Rogers, T. I. Richardson, Acc. Chem. Res. 1998, 31, 9-17.
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    • The same ee has been reported for this reaction by Barbas and co-workers, who obtained the aldol product in 60 % yield:, K. Sakthivel, W. Notz, T. Bui, C. F. Barbas, III, J. Am. Chem. Soc. 2001, 123, 5260-5267. In our synthesis of doliculide (1), only 26 obtained from 14 was processed in the aldol reaction with methacrolein (25).
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    • CCDC-1047307 contains the supplementary crystallographic data for this paper (compound 24). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data-request/cif.
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    • The all-syn arrangement of the methyl groups on C2, C4, and C6 was further confirmed by an NMR spectroscopy method recently developed by Breit and co-workers that is based on the differences in chemical shifts between the vicinal protons attached to the carbon atoms connecting the chiral centers in polydeoxypropionates:, Y. Schmidt, K. Lehr, L. Colas, B. Breit, Chem. Eur. J. 2012, 18, 7071-7081.
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    • Schmidt, Y.1    Lehr, K.2    Colas, L.3    Breit, B.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.