Total Syntheses of Vellosimine, N-Methylvellosimine, and 10-Methoxyvellosimine and Formal Synthesis of 16-Epinormacusine B through a [5+2] Cycloaddition

被引：20
作者：
Krueger, Sebastian [2 ]
Gaich, Tanja [1 ]
机构：
[1] Univ Konstanz, Lehrstuhl Organ Chem, Univ Str 10, D-78457 Constance, Germany
[2] Leibniz Univ Hannover, Inst Organ Chem, Schneiderberg 1 B, D-30167 Hannover, Germany
来源：
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 2016卷 / 28期
关键词：
Total synthesis; Natural products; Alkaloids; Asymmetric synthesis; Cycloaddition; Ring expansion; ENANTIOSPECIFIC TOTAL-SYNTHESIS; INDOLE ALKALOIDS; GENERAL-APPROACH; 1,3-DIPOLAR CYCLOADDITION; AJMALINE ALKALOIDS; VINYL HALIDES; SARPAGINE; BIOSYNTHESIS; RAUVOLFIA; 3-OXIDOPYRIDINIUM;
D O I：
10.1002/ejoc.201600870
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
To date, more than 100 members of the sarpagine alkaloid family have been isolated. Their structural variations originate from oxidative transformations of the carboskeleton and the presence of both absolute configurations at the C-16 atom, which is established in the course of their biosynthesis. More than 40 sarpagine alkaloids belong to the either the 16-regular or 16-epi subgroups, depending on the stereochemistry at C-16. Herein, we report the formal synthesis of 16-epinormacusine B, a member of the 16-epi group, by using our well-established generalized strategy for the total synthesis of these alkaloids. Furthermore, we provide the synthetic details and pitfalls of the asymmetric total syntheses of vellosimine, N-methylvellosimine, and 10-methoxyvellosimine, all members of the 16-regular group.
引用
收藏
页码：4893 / 4899
页数：7
相关论文
共 52 条
  • [1] Highly diastereoselective 1,3-dipolar cycloaddition reactions of trans-2-methylene-1,3-dithiolane 1,3-dioxide with 3-oxidopyridinium and 3-oxidopyrylium betaines:: a route to the tropane skeleton
    Aggarwal, VK
    Grainger, RS
    Newton, GK
    Spargo, PL
    Hobson, AD
    Adams, H
    [J]. ORGANIC & BIOMOLECULAR CHEMISTRY, 2003, 1 (11) : 1884 - 1893
  • [2] (1R,3R)-2-METHYLENE-1,3-DITHIOLANE 1,3-DIOXIDE - A HIGHLY REACTIVE AND HIGHLY SELECTIVE CHIRAL KETENE EQUIVALENT
    AGGARWAL, VK
    DRABOWICZ, J
    GRAINGER, RS
    GULTEKIN, Z
    LIGHTOWLER, M
    SPARGO, PL
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (16) : 4962 - 4963
  • [3] [Anonymous], 2008, Angew. Chem.
  • [4] The total synthesis of (-)-lemonomycin
    Ashley, ER
    Cruz, EG
    Stoltz, BM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (49) : 15000 - 15001
  • [5] Burghardt T.E., 2005, J. Sulfur Chem, V26, P411, DOI DOI 10.1080/17415990500195198
  • [6] Stereospecific Approach to the Synthesis of Ring-A Oxygenated Sarpagine Indole Alkaloids. Total Synthesis of the Dimeric Indole Alkaloid P-(+)-Dispegatrine and Six Other Monomeric Indole Alkaloids
    Edwankar, Chitra R.
    Edwankar, Rahul V.
    Namjoshi, Ojas A.
    Liao, Xuebin
    Cook, James M.
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2013, 78 (13) : 6471 - 6487
  • [7] Deprotecting dithiane-containing alkaloids
    Fleming, FF
    Funk, L
    Altundas, R
    Tu, Y
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (19) : 6502 - 6504
  • [8] Aspidospermatan-aspidospermatan and eburnane-sarpagine bisindole alkaloids from Leuconotis
    Gan, Chew-Yan
    Low, Yun-Yee
    Robinson, Ward T.
    Komiyama, Kanki
    Kam, Toh-Seok
    [J]. PHYTOCHEMISTRY, 2010, 71 (11-12) : 1365 - 1370
  • [9] Mild, Efficient, and Greener Dethioacetalization Protocol Using 30% Hydrogen Peroxide in Catalytic Combination with Ammonium Iodide
    Ganguly, Nemai C.
    Mondal, Pallab
    [J]. SYNTHETIC COMMUNICATIONS, 2011, 41 (16) : 2374 - 2384
  • [10] Rauvotetraphyllines A-E, new indole alkaloids from Rauvolfia tetraphylla
    Gao Y.
    Zhou D.-S.
    Kong L.-M.
    Hai P.
    Li Y.
    Wang F.
    Liu J.-K.
    [J]. Natural Products and Bioprospecting, 2012, 2 (2) : 65 - 69
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