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    Sysoiev Nakadomarin-A Problem

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    1) The document describes a scalable total synthesis of (-)-nakadomarin A in 17 steps from commercially available starting materials. 2) Key steps include installing the tetrasubstituted olefin through a Heck reaction and coupling of fragments I and II. 3) Final steps involve deprotection and oxidation to yield the natural product (-)-nakadomarin A.

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    Sysoiev Nakadomarin-A Problem

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    41 views1 page
    1) The document describes a scalable total synthesis of (-)-nakadomarin A in 17 steps from commercially available starting materials. 2) Key steps include installing the tetrasubstituted olefin through a Heck reaction and coupling of fragments I and II. 3) Final steps involve deprotection and oxidation to yield the natural product (-)-nakadomarin A.

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    Total Synthesis Problem

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    1) The document describes a scalable total synthesis of (-)-nakadomarin A in 17 steps from commercially available starting materials. 2) Key steps include installing the tetrasubstituted olefin through a Heck reaction and coupling of fragments I and II. 3) Final steps involve deprotection and oxidation to yield the natural product (-)-nakadomarin A.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    41 views1 page

    Sysoiev Nakadomarin-A Problem

    Uploaded by

    abc
    1) The document describes a scalable total synthesis of (-)-nakadomarin A in 17 steps from commercially available starting materials. 2) Key steps include installing the tetrasubstituted olefin through a Heck reaction and coupling of fragments I and II. 3) Final steps involve deprotection and oxidation to yield the natural product (-)-nakadomarin A.

    Copyright:

    © All Rights Reserved
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    of 1

    Denksport

    A scalable total synthesis of (-)-nakadomarin A R. K. Boeckman, Jr. et al., Org. Lett. 2016, 18, 6136-6139
    08.03.2017
    Dima 1) (R)-CBS (20mol%)
    BH3*SMe2, DCM
    O 3) NaH, toluene,
    20 h, 98%, 95% ee reflux, 12 h, 3:1 dr
    TBSO CO2iPr
    2) I, DMAP, py, 4) LiAl(tBu)2(OtBu)H, THF
    SO2Ph DCM, 273K, 3 h 273K to rt, 12 h
    95%
    50% (2 steps)

    5) TMSN3, PPh3 8) LDA, ClCO2Me, THF


    toluene, rt, 2 h 6) TBAF, THF, 273K, 1 h, 90% 195K, 4 h, 90%

    then 14, rt, 10 h 7) TPAP, NMO, DCM


    9) hept-5-yn-1-amine, MeOH
    then reflux, 48 h MS, 3 h, rt, 85%
    323K, 12 h, 95%
    90%

    a) NaH, nBuLi, THF


    c) 1M HCl, H2O/EtOH e) II, LDA, THF
    273K, 30 min
    O O then 1-bromo-2-butyne, 2h 338K, 24 h, 80% rt, 12 h
    P(OMe)2 then aq. 1N HCl
    Me b) NaH, 1,3-diacetoxy- d) (COCl)2, DMSO
    acetone, THF, 273K to rt PE, 86%
    Et3N, 195K to rt, 85%
    76%

    10) III, PhCO2H (10mol%) 11) BF3*OEt2, Et3SiH


    MS, DCM, rt, 18 h DCM, rt, 12 h, 76%
    73% brsm yield
    85% conversion
    H 13) IV (5mol%)
    15) TFA ZnCl2 (5mol%) 12) LiEt3BH
    N 16) Li/NH3 toluene, MS
    O Et3SiH, DCM DCM
    (NH4)2SO4 253K, 2 h 18 h, rt 303K, 2 h
    H H
    N 17) tBuOH then DIBAL-H 14) H2, quinoline then acetone
    THF, 195K DCM Lindlar's cat. Tf2O, rt
    1h, 75% 253K, 60% EtOAc, 1h, rt 2h, 76%
    OMe
    82% (2 steps)

    (-)-nakadomarin A

    OSiPh3
    Ph3SiO Mo OSiPh3
    O O Me Ph
    N N
    Ph
    Cl O (EtO)2P N N
    N Me OTMS
    H
    I II III IV

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