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两种3-酰基-5,6-二氢-2H-吡喃酮的不对称全合成：(R)-足芽素-S和(R)-lachnelluloic酸以及(-)-lachnelluloic酸绝对构型的验证

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.

作者信息

Fujiwara Tetsuya, Tsutsumi Takeshi, Nakata Kohei, Nakatsuji Hidefumi, Tanabe Yoo

机构信息

Department of Chemistry, School of Science and Technology, Kwansei Gakuin University, Sanda, Hyogo 669- 1337, Japan.

出版信息

Molecules. 2017 Jan 1;22(1):69. doi: 10.3390/molecules22010069.

DOI:10.3390/molecules22010069
PMID:28045445
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6155883/
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 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.

摘要

实现了对天然3-酰基-5,6-二氢-2H-吡喃-2-酮的代表物（R）-足母细胞蛋白-S和（R）-lachnelluloic酸的便捷不对称全合成。与已报道的（R）-足母细胞蛋白-S的全合成（14步，总产率5%）相比，本研究仅用五步就完成了，总产率为40%，对映体过量值（ee）为98%（高效液相色谱分析）。采用类似策略，首次实现了相关（R）-lachnelluloic酸的不对称全合成，总产率为40%，ee为98%（高效液相色谱分析）。关键步骤利用了易于获得且可靠的Soriente和Scettri的Ti(OiPr)₄/(S)-联萘酚催化的不对称Mukaiyama羟醛加成反应，该反应以乙酰乙酸乙酯与正丁醛反应生成的1,3-双（三甲基硅氧基）二烯用于合成（R）-足母细胞蛋白-S，与正戊醛反应生成的1,3-双（三甲基硅氧基）二烯用于合成（R）-lachnelluloic酸。通过比较天然产物和合成样品的比旋光度值，明确阐明了（-）-lachnelluloic酸C(6)位迄今未知的绝对构型为6R。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/7f43de47dc4d/molecules-22-00069-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/fa88280b6182/molecules-22-00069-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/ddbe14d7bafa/molecules-22-00069-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/031edc762cf2/molecules-22-00069-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/016667288f2f/molecules-22-00069-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/7f43de47dc4d/molecules-22-00069-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/fa88280b6182/molecules-22-00069-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/ddbe14d7bafa/molecules-22-00069-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/031edc762cf2/molecules-22-00069-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/016667288f2f/molecules-22-00069-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8424/6155883/7f43de47dc4d/molecules-22-00069-sch003.jpg

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