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Keywords = 3-acyl-5,6-dihydro-2H-pyrones

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9 pages, 1563 KiB  
Article
Asymmetric Total Syntheses of Two 3-Acyl-5,6- dihydro-2H-pyrones: (R)-Podoblastin-S and (R)- Lachnelluloic Acid with Verification of the Absolute Configuration of (−)-Lachnelluloic Acid
by Tetsuya Fujiwara, Takeshi Tsutsumi, Kohei Nakata, Hidefumi Nakatsuji and Yoo Tanabe
Molecules 2017, 22(1), 69; https://doi.org/10.3390/molecules22010069 - 1 Jan 2017
Cited by 9 | Viewed by 6454
Abstract
Expedient asymmetric total syntheses of both (R)-podoblastin-S and (R)-lachnelluloic acid, representative of natural 3-acyl-5,6-dihydro-2H-pyran-2-ones, were performed. Compared with the reported total synthesis of (R)-podoblastin-S (14 steps, overall 5% yield), the present study was achieved in only five [...] Read more.
Expedient asymmetric total syntheses of both (R)-podoblastin-S and (R)-lachnelluloic acid, representative of natural 3-acyl-5,6-dihydro-2H-pyran-2-ones, were performed. Compared with the reported total synthesis of (R)-podoblastin-S (14 steps, overall 5% yield), the present study was achieved in only five steps in an overall 40% yield and with 98% ee (HPLC analysis). In a similar strategy, the first asymmetric total synthesis of the relevant (R)-lachnelluloic acid was achieved in an overall 40% yield with 98% ee (HPLC analysis). The crucial step utilized readily accessible and reliable Soriente and Scettri’s Ti(OiPr)4/(S)-BINOL‒catalyzed asymmetric Mukaiyama aldol addition of 1,3-bis(trimethylsiloxy)diene, derived from ethyl acetoacetate with n-butanal for (R)- podoblastin-S and n-pentanal for (R)-lachnelluloic acid. With the comparison of the specific rotation values between the natural product and the synthetic specimen, the hitherto unknown absolute configuration at the C(6) position of (−)-lachnelluloic acid was unambiguously elucidated as 6R. Full article
(This article belongs to the Special Issue Asymmetric Synthesis 2017)
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