conrotatory Metal Catalyzed Cyclization .conrotatory Metal Catalyzed Cyclization oof pEenynesning?

  • View
    215

  • Download
    0

Embed Size (px)

Text of conrotatory Metal Catalyzed Cyclization .conrotatory Metal Catalyzed Cyclization oof pEenynesning?

  • ZR

    [M]+

    Z

    R'

    Alder-ene cycloisomerization

    Z

    R =

    Z = NTs, O

    Z

    R

    Z

    R

    Z

    R

    Skeletal Rearrangement

    ZR

    R'OHOR'

    Alkoxycyclization

    conrotatory opening?

    Metal Catalyzed Cyclization of Enynes

    B. M. Trost

    P. A. Wender

    A. Frstner, N. Chatani, M. Malacria, A. S. K. Hashmi, F. D. Toste, F. Gagosz, S. Kozmin, S. P. Nolan

  • Metal-Catalyzed Skeletal Rearrangement of Enynes: Mechanistic Pathways

    MXn

    RZ

    Z

    H

    R

    H

    MXn

    Z

    R

    Z

    R- MXn

    +

    singlecleavage

    doublecleavage

    Z

    H

    - MXn

    R

    H

    conrotatory opening

    Z MXn

    HR

    H

    - MXn

    Z

    R

    MXn

    Z

    H

    - MXn

    R'

    Metal-catalyzedAlder-enecyclosiomerization

  • Metal Catalyzed Cyclization of Enynes

    Chem. Eur. J. 2003, 9, 2627.

    TSexo

    10.3

    19.5O

    C

    C

    ClC

    Pt

    C

    Cl

    C

    C

    C

    C

    CC C

    C

    C

    C

    C

    Cl

    C

    Pt

    O

    Cl

    C

    C

    CC

    C

    C

    O

    C

    Pt

    Cl

    C

    Cl

    HMe

    Pt

    Cl

    Cl

    OH2

    =

    exo

    TSendo

    11.2

    8.1

    Cl

    O

    Pt

    C

    C

    C

    C

    C

    C

    C

    C

    Cl

    ClO

    Pt

    C

    C

    C

    C

    C

    Cl

    C

    C

    C

    endo

  • Metal Catalyzed Cyclization of Enynes

    MXn

    Z

    H

    R

    H

    MXn

    RZ

    a

    b

    Z

    HOR'

    HR

    Z

    R

    OR'

    5-exo-dig

    a

    R'OH

    R'OH

    b

    RZ

    MXn

    Z

    MXn

    H

    H

    R

    H

    Z

    H

    H

    R

    H

    Z

    H

    OR'

    HR

    Z R

    OR'

    b a6-endo-dig

    R'OHa

    R'OH

    b

    Chem. Eur. J. 2003, 9, 2627

  • Pt(II) vs. Au(I) as Catalysts

    TSexoTSendo

    10.3

    19.5

    11.2

    8.1exo

    endo

    Pt(L)Cl2

    Pt(L)Cl2Cl2(L)Pt

    Pt(L)Cl2

    Cl2(L)Pt

    L = H2O

    PtCl2

    TSexo

    TSendo

    0.1

    exo

    endo

    Au

    Au

    PH3

    Au

    H3P

    AuPH3

    AuH3P

    [Au(PH3)]+

    PH3

    6.2

    13.4

    6.1

  • Au(I)-Catalyzed Cyclization of Enynes: Alkoxycyclizations

    Angew. Chem. Int. Ed. 2004, 43, 2402.

    Ph3PAuMe, TFA

    MeOH, 23C, 30 min

    (95%)

    MeO2C

    MeO2C

    OMe

    MeO2C

    MeO2C

    OMe

    OMe

    Ph3PAuMe, H3PW12O40

    MeOH, 56C, 17 h

    (96%)

    PhO2S

    PhO2S

    PhPhO2S

    PhO2SOMe

    Ph

    HO

    Ph

    Ph3PAuMe, H3PW12O40

    toluene, 23C, 3 h

    (100%)

    O

    HPh

    H

  • Au(I)-Catalyzed Cyclization of Enynes: Skeletal Rearrangements

    Angew. Chem. Int. Ed. 2004, 43, 2402.

    CH2Cl2, 23C, 10 min

    MeO2C

    MeO2CMeO2C

    MeO2C

    (96%)

    CH2Cl2, 23C, 25 min

    (91%)

    MeO2C

    MeO2C

    MeO2C

    MeO2C

    CH2Cl2, 23C, 15 min

    PhO2S

    PhO2SPhO2S

    PhO2S

    Ph3PAuCl / AgSbF6

    Ph3PAuCl / AgBF4

    Ph3PAuCl / AgBF4

    Ph3PAuCl / AgSbF6

    CH2Cl2, 23C, 5 min

    (67%)

    MeO2C

    MeO2C

    MeO2C

    MeO2C OH

    OH

    (100%)

  • New Au(I) Complexes

    C. Nieto-Oberhuber

    N NR R'

    R = R' = MesR = Mes, R' = MeR = R' = Me

    Au

    Cl

    R = Cy, R' = HR = t-Bu, R' = HR = Cy, R' = i-Pr

    P Au Cl

    R R

    R'

    R'

    R'

    P Au Cl

    Cy Cy

    MeO

    MeO

    R = Cy, t-Bu

    P Au NCMe

    R R SbF6

  • New Au(I) Complexes

    R = Cy, t-Bu

    P Au (ArH)

    RR SbF6

    Angew. Chem. Int. Ed. 2006, 45, 5455.

  • New Au(I) Complexes

    electrophilicity

    AuCl

    N NR R'

    R = R' = MesR = Mes, R' = MeR = R' = Me

    Au

    Cl

    / AgSbF6R = Cy, t-Bu

    P Au NCMe

    R R SbF6

    [Au(PPh3)(MeCN)]+SbF6

    -

    O P3

    Au Cl

    / AgSbF6

  • Metal-Catalyzed Skeletal Rearrangement of Enynes: Mechanistic Pathways

    - [Au(PH3)] Me

    single cleavage

    Ea = 0.1 kcalmol-1

    !G = -0.7 kcalmol-1

    - [Au(PH3)]

    Me

    double cleavage

    Me

    H

    AuH3P

    B3LYP/6-31G(d), LANL2DZ (Au) (E kcal mol-1).

    Au

    transition state for the double rearrangement

    Au

    H3P

    Me

    H

    Au

    PH3

    MeH

    H

    Me

    [Au(PH3)]

    Ea = 9.1 kcalmol-1

    !G = 2.7 kcalmol-1

    Angew. Chem. Int. Ed. 2005, 44, 6146.

  • Au(I)-Catalyzed Biscyclopropanation of Dienynes

    H

    CH2Cl2, 23C, 5 min

    R

    R R

    R

    [Au(PPh3)(MeCN)]+SbF6

    -

    R = CO2Me (98%)

    R = SO2Ph (100%)

    R = CH2OAc (96%)

    (2 mol%)

    HMeO2C CO2Me

    MeO2C

    MeO2C

    MeO2C

    MeO2C

    CO2Me

    CO2MeCH2Cl2, 23C, 5 min

    [Au(PPh3)(MeCN)]+SbF6

    -

    (2 mol%)

    (88%)

    Chem. Eur. J. 2006, 12, 1694.

  • Au(I)-Catalyzed Biscyclopropanation of Dienynes

    Chem. Eur. J. 2006, 12, 1694.

    L-Au

    L-Au

    H

    H

    H

    1.8

    6.6

    2.9

    13.2

    anti

  • Au(I)-Catalyzed Intermolecular Cyclopropanation

    Ph

    H

    MeO2C

    MeO2C MeO2C

    MeO2C

    Ph

    H+

    CH2Cl2, -40 to 0C

    (94%)

    N NMes Mes

    AuCl / AgSbF6

    PhH

    H

    H

    (77%)

    PhH

    H

    H

    (76%)

    Ph

    H

    H

    (60%, 5:1)

    TsN

    PhH

    H

    H

    (75%)

    TsN

    PhH

    H

    H

    (73%)

    Me

    H

    (53%)

    MeO2C MeO2C MeO2C

    PhO2S

    MeO2C MeO2C MeO2C

    PhO2S

    Angew. Chem. Int. Ed. 2006, 45, anie.200602448.

    H

  • Au(I)-Catalyzed Intermolecular Cyclopropanation

    Au(L)

    R

    R

    R

    - Au(L)+

    R

    (L)Au

    H

    H

    Au(L)

    R

    H

    H

    Au(L)

    RH

    H

    - Au(L)+

    Angew. Chem. Int. Ed. 2006, 45, anie.200602448.

    tBu

    tBu

    O P AuCl3

    / AgSbF6

    -50 to 23C

    ZZ = C(CO2Me)2

    Ph

    Z

    Ph

    (67%, 3.3:1 cis/trans)

  • Au(I) Metallotropic Shift

    Z

    [AuL]Z

    MeH

    Z

    Z

    MeH

    [AuL]

    Me Me

    [Au(L)]

    [1,3]-Metallotropic shift

    Angew. Chem. Int. Ed. 2006, 45, anie.200602448.

    CH2Cl2, 23C

    / AgSbF6

    tBu

    tBu

    O P AuCl3Z

    Z = C(CO2Me)22 : 1

    Z

    Z

    H

    Z

    Me

    Me

    H

    Z

    H

    Z

    Me

    Me

    H

    Me Me

    +(2 mol%)

  • [4+2] Cycloaddition of Arylenynes

    J. Am. Chem. Soc. 2005, 127, 6178-6179

    Z

    R1

    Z

    HCH2Cl2, r.t.

    R1R2

    R2

    R3

    R3[Au(L)Cl], AgSbF6

    H

    MeO2C

    MeO2C

    (86%)

    H PhH

    MeO2C

    MeO2C

    (67%)

    H

    MeO2C

    MeO2C

    (77%)

    OMeH

    MeO2C

    MeO2C

    (74%)

    NO2

    H

    MeO2C

    MeO2C

    (95%)

    H

    MeO2C

    MeO2C

    (65%)

    OMe

    H PhH

    MeO2C

    MeO2C

    (80%)

    Ph

    H PhH

    MeO2C

    MeO2C

    (58%)

    NO2

    H

    MeO2C

    MeO2C

    (73%)

  • Cyclopropane to Cyclobutanone Ring Expansion

    Z

    HH

    OR

    [Au(L)]

    Z

    H

    H

    [Au(L)]

    OR

    - [Au(L)][Au(L)]

    CH2Cl2, MeOH (2 equiv)r.t., 5 min

    P Au NCMet-Bu t-Bu SbF6

    OR

    O

    H

    H

    E. Jimnez-Nez, C. Claverie

    R = TMS (98%)R = TBS (100%)

    MeO2C

    MeO2C

    MeO2C

    MeO2C

  • Cyclopropane to Cyclobutanone Ring Expansion and Prins Cyclization

    CH2Cl2, r.t., 5 min

    P Au NCMet-Bu t-Bu SbF6

    E. Jimnez-Nez, C. Claverie

    Z

    OEt

    Z O

    H

    H

    Z = C(CO2Me)2 (11%) (69%, anti/syn = 1.3:1)

    Z = --- (54%, anti/syn = 3.2:1)

    + ZOEt

    HH

    O

    O

    H

    H

    OH

    OH

    O

    Sulcatine G

    Z

    HH

    OEt

    [Au(L)]

    PrinsZ

    OEt

    HH

    [Au(L)]

  • Gold-Prins Reaction

    Angew. Chem. Int. Ed. 2006, 45, 5452.

    CH2Cl2, rt, 30 min

    Z = C(CO2Me)2

    ZO

    HZ

    H

    O ZO

    MeMe

    Me

    HH

    +

    (58%) (18%)

    AuCl

    Z

    HMe

    ClAu

    O

    H

    AuCl

    Z

    H

    O

    Me

    AuClH

    Z

    H

    O

    Me

    H

    AuCl

    - AuCl

  • Gold-Prins Reaction

    O

    Me

    Me

    Me

    OHH

    HOMe

    H

    Orientalol E

    CH2Cl2, rt, 30 min

    AuClZO

    MeZ

    H

    O ZO

    MeMe

    Me

    MeMe

    +

    (79%) (10%)

    ZO

    i-PrZ

    H

    O ZO

    MeMe

    Me

    i-Pri-Pr

    +

    (84%) (12%)

    CH2Cl2, rt, 30 min

    AuCl

    Z

    Me

    O

    Me

    Me

    [Au(L*)L']SbF6CH2Cl2, rt, 5 min

    Angew. Chem. Int. Ed. 2006, 45, 5452.

    P Au NCMe

    t-But-Bu SbF6

    [Au(L*)L']SbF6 =

  • Arylation of Alkynes

    AuCl3CH2Cl2, 23C, 1 h

    NH

    N

    R SO2Ar

    R = CO2Me, Ar = 2,4-(NO2)2C6H3 30 min (75%)

    R = H, Ar = Ph 24 h (55%)

    N

    N

    O

    MeO

    CO2Me

    Lundurine A

    Angew. Chem. Int. Ed. 2006, 45, 1105.

    NH

    N SO2Ar

    NH

    NSO2Ar

    CH2Cl2, 23C

    P Au NCMe

    t-But-Bu SbF6

    (5 mol%)R R

    R = CO2Me, Ar = 2,4-(NO2)2C6H3 30 min (82%)

    R = H, Ar = Ph 16 h (65%)

  • Arylation