공업화학 (Applied Chemistry for Engineering)

  • 제31권2호
  • /
  • Pages.187-192
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  • 2020
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  • 1225-0112(pISSN)
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  • 2288-4505(eISSN)
한국공업화학회 (The Korean Society of Industrial and Engineering Chemistry)
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(2S,3R)-3-하이드록시호모세린락톤의 입체선택적 합성 : 바이닐글라이신 OBO Ester 유도체의 입체선택적인 이중알콜화 반응

Stereoselective Synthesis of (2S,3R)-3-Hydroxyhomoserine Lactone via anti Selective Dihydroxylation of an OBO Group-Protected Vinyl Glycine Analog

  • 고무현 (서울대학교 공과대학 화학생물공학부) ;
  • 전종호 (경북대학교 공과대학 응용화학공학부 응용화학전공) ;
  • 김영규 (서울대학교 공과대학 화학생물공학부)
  • Koh, Moo-hyun (School of Chemical and Biological Engineering, Seoul National University) ;
  • Jeon, Jongho (Department of Applied Chemistry, School of Applied Chemical Engineering, Kyungpook National University) ;
  • Kim, Young Gyu (School of Chemical and Biological Engineering, Seoul National University)
  • 투고 : 2020.03.04
  • 심사 : 2020.03.11
  • 발행 : 2020.04.10
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⟨ 이전 논문 다음 논문 ⟩

초록

(2S,3R)-3-hydroxyhomoserine lactone (HSL)은 생리학적 활성을 가지는 다양한 종류의 화합물을 합성하기 위한 중간체로 활용되어 왔다. 본 논문에서는 OBO ester로 보호된 바이닐글라이신 유도체에 이중알콜화 반응을 수행하여 효율적인 HSL 합성 결과를 보고하고자 한다. 바이닐글라이신의 비고리 conformation은 크기가 큰 OBO ester에 의해 조절되었으며 N-inside conformation을 통해 이중알콜화 반응이 진행됨으로써 높은 anti 선택성(> 10 : 1)을 얻을 수 있었다. 이러한 결과를 바탕으로 N-Cbz-L-serine을 출발물질로 사용하여 총 7단계 34%의 수율로 HSL을 합성할 수 있었다. 본 연구의 결과는 amino diol 구조를 가지는 다양한 생리활성 천연물들의 입체선택적인 합성에 유용하게 활용될 수 있을 것으로 기대된다.

(2S,3R)-3-hydroxyhomoserine lactone (HSL) has been used as a key intermediate for the synthesis of various biologically active compounds. In this study, we demonstrated an efficient synthesis of HSL via anti selective dihydroxylation of a protected vinyl glycine analog with an oxabicyclo[2.2.2]octyl orthoester (OBO) ester group. Because the acyclic conformation of the substrate was efficiently controlled by the bulky OBO ester group, a diastereoselectivity of > 10 : 1 was obtained in the dihydroxylation reaction without the use of a chiral reagent. By using this result, the target compound 1 can be obtained from commercially available N-Cbz-L-serine 2 in seven steps with an overall yeid of 34%. This result could be applied to the stereoselective synthesis of biologically active molecules containing a vicinal amino diol moiety.

키워드

참고문헌

  1. C.-X. Ye, Y. Y. Melcamu, H.-H. Li, J.-T. Cheng, T.-T. Zhang, Y.-P. Ruan, X. Zheng, X. Lu, and P.-Q. Huang, Dual catalysis for enantioselective convergent synthesis of enantiopure vicinal amino alcohols, Nat. Commun., 9, 410-418 (2018). https://doi.org/10.1038/s41467-017-02698-4
  2. M. M. Heravi, T. B. Lashaki, B. Fattahi, and V. Zadsirjan, Application of asymmetric Sharplessaminohydroxylation in total synthesis of natural products and some synthetic complex bio-active molecules, RSC Adv., 8, 6634-6659 (2018). https://doi.org/10.1039/C7RA12625E
  3. O. K. Karjalainen and A. M. P. Koskinen, Diastereoselective synthesis of vicinal amino alcohols, Org. Biomol. Chem., 10, 4311-4326 (2012). https://doi.org/10.1039/c2ob25357g
  4. J. Jeon, N. Shin, and Y. G. Kim, Stereocontrolled dihydroxylation reactions of acyclic allylic amines, Appl. Chem. Eng., 25, 437-446 (2014). https://doi.org/10.14478/ace.2014.1113
  5. J. S. Oh, D. Y. Park, B. S. Song, J. G. Bae, S. W. Yoon, and Y. G. Kim, anti Selective dihydroxylation by the ketimine derivatives of the allylic amine in monosubstituted olefins, Tetrahedron Lett., 43, 7209-7212 (2002). https://doi.org/10.1016/S0040-4039(02)01654-4
  6. J. S. Oh, J. Jeon, D. Y. Park, and Y. G. Kim, Stereoselective dihydroxylation reactions of reactions of ${\gamma}$-amino-${\alpha},{\beta}$-unsaturated esters via their aryl ketimine derivatives, Chem. Commun., 41, 770-771 (2005).
  7. J. Jeon, S.-K. Hong, J. S. Oh, and Y. G. Kim, Stereoselective synthesis of protected (2R,3R,4S)-4,7-diamino-2,3-dihydroxyheptanoic acid: A novel amino acid of callipeltins A and D, J. Org. Chem., 71, 3310-3313 (2006). https://doi.org/10.1021/jo052676o
  8. J. Jeon, J. H. Lee, J.-W. Kim, and Y. G. Kim, syn-Selective dihydroxylation of ${\gamma}$-amino-${\alpha},{\beta}$-unsaturated (Z)-esters from D-serine: Stereoselective synthesis of D-iminolyxitol, Tetrahedron: Asymmetry, 18, 2448-2453 (2007). https://doi.org/10.1016/j.tetasy.2007.10.004
  9. J. Jeon, N. Shin, J. H. Lee, and Y. G. Kim, Efficient stereo-selective synthesis of (2S,3S,4S)-3,4-dihydroxyglutamic acid, Appl. Chem. Eng., 25, 392-395 (2014). https://doi.org/10.14478/ace.2014.1045
  10. J. Jeon, M. Shin, J. W. Yoo, J. S. Oh, J. G. Bae, S. H. Jung, and Y. G. Kim, Highly anti-selective dihydroxylation of 1,2-dialkyl substituted (Z)-allylic amines: Stereoselective synthesis of a D-ribo-phytosphingosine derivative, Tetrahedron Lett., 48, 1105-1108 (2007). https://doi.org/10.1016/j.tetlet.2006.12.084
  11. J. Jeon, S.-H Kim, J. H. Lee, and Y. G. Kim, anti-Selective dihydroxylations of monosubstituted allylic amine and ${\gamma}$-amino-${\alpha},{\beta}$-unsaturated (E)-esters by bulky alkyl groups, Bull. Korean Chem. Soc., 30, 1003-1008 (2009). https://doi.org/10.5012/bkcs.2009.30.5.1003
  12. M. A. Blaskovich and G. A. Lajoie, Synthesis of a chiral serine aldehyde equivalent and its conversion to chiral ${\alpha}$-amino acid derivatives, J. Am. Chem. Soc., 115, 5021-5030 (1993). https://doi.org/10.1021/ja00065a010
  13. M. A. Blaskovich, G. Evindar, N. G. W. Rose, S. Wilkinson, Y. Luo, and G. A. Lajoie, Stereoselectivesynthesis of threo and erythro ${\beta}$-hydroxyand ${\beta}$-disubstituted-${\beta}$-hydroxy ${\alpha}$-amino acids, J. Org. Chem., 63, 3631-3646 (1998). https://doi.org/10.1021/jo972294l
  14. D. B. Hansen, X. Wan, P. J. Carroll, and M. M. Joullie, Stereoselectivesynthesis of four stereoisomers of ${\beta}$-methoxytyrosine, a component of callipeltin A, J. Org. Chem., 70, 3120-3126 (2005). https://doi.org/10.1021/jo047876z
  15. K. N. Houk, H. Y. Duh, Y. D. Wu, and S. R. Moses, Steric models for stereoselectivity of nitrile oxide cycloadditions to chiral alkenes, J. Am. Chem. Soc., 108, 2754-2755 (1986). https://doi.org/10.1021/ja00270a044
  16. M. Koh, anti-Selective dihydroxylation of an OBO ester derivative of vinyl glycine: Application to stereoselective synthesis of (2S,3R)-3-hydroxyhomoserine lactone, Ph. D. Dissertation, Seoul National University, Seoul, Republic of Korea (2009).
  17. M. C. Pirrung, D. S. Nunn, and A. T. McPhail, Synthesis and absolute configuration of hydroxythreonine, a biosynthetic precursor of rhizobitoxine in pseudomonas, Bioorg. Med. Chem. Lett., 3, 2095-2098 (1993). https://doi.org/10.1016/S0960-894X(01)81024-6
  18. J. A. Olsen, R. Severinsen, T. B. Rasmussen, M. Hentzer, M. Givskov, and J. Nielsen, Synthesis of new 3- and 4-substituted analogues of acyl homoserine lactone quorum sensing autoinducers, Bioorg. Med. Chem. Lett., 12, 325-328 (2002). https://doi.org/10.1016/S0960-894X(01)00756-9
  19. M. Ikunaka, J. Matsumoto, Y. Fujima, and Y. Hirayama, An enantioselective synthesis of (2S,3R)-3-(N-benzyloxycarbonyl)amino-1-chloro-4-phenylthiobutan-2-ol, a central intermediate of Nelfinavir, Org. Process Res. Dev., 6, 49-53 (2002). https://doi.org/10.1021/op010073i
  20. V. P. Vassilev, T. Uchiyama, T. Kajimoto, and C.-H. Wong, An efficient chemo-enzymatic synthesis of ${\alpha}$-amino-${\beta}$-hydroxy-${\gamma}$-butyrolactone, Tetrahedron Lett., 28, 5063-5064 (1995). https://doi.org/10.1016/S0040-4039(00)95590-4