COORDINATION CHEMISTRY AT CARBON - Startseite .coordination chemistry at carbon ... c2 c20 c19 c7

  • View
    213

  • Download
    0

Embed Size (px)

Text of COORDINATION CHEMISTRY AT CARBON - Startseite .coordination chemistry at carbon ... c2 c20 c19 c7

  • COORDINATION CHEMISTRY AT CARBON

  • COORDINATION CHEMISTRY AT CARBON

    A. F. with M. Alcarazo, C. W. Lehmann, A. Anoop, W. Thiel, Nature Chemistry 2009, 1, 295

    Cl2

    Cl1

    C16

    C15

    C17

    Au2

    Au1

    Cl4

    C14

    C25

    C18

    C3

    C13

    C4

    C1

    O1

    Cl3

    P4

    C2

    C20

    C19

    C7

    C21

    O2

    C8

    C12C9

    C11

    C5

    C24

    C10

    C22

    C23

    C6

  • F2

    F1

    F4Sb1F5

    F6

    F3

    C7

    C6

    N2

    C10

    C9

    C5

    C2

    C23N4

    C3

    C1

    N3

    N1

    C22

    C24C11

    C8

    Au1

    C21

    C25

    C4

    C26

    P1

    C46

    C31

    C41

    C36

    C32

    C45

    C35

    C33

    C42

    C34

    C44

    C43

    A. Frstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. Int. Ed. 2008, 47, 3210

    for a large scale synthesis of tetrakis(dimethylamino)allene, see:

    A. Frstner, M. Alcarazo, H. Krause, Org. Synth. 2009, 86, 298

  • C25

    C24

    C26

    C23

    C21

    C22

    C35

    C34

    C36

    C33

    C31

    C32

    P1

    C12

    C11

    C13

    Au1

    C14

    C16

    C8

    C4

    C15

    N3

    C5

    C2

    N6

    C1

    C7

    ENDIAMINE LIGANDS

    A. Frstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. Int. Ed. 2008, 47, 3210

  • C12

    C8 C7

    N1C2

    C1

    C9

    C4

    C3

    C6

    N2

    C5

    O1

    C13

    C10 C11

    C43

    C44

    C42

    C45

    C35

    C36

    C3

    C41

    C46

    C34

    C2

    C5

    N2

    C31

    P1

    C33

    N1

    C1

    C32

    Au1

    C26

    C4C21

    C6

    F3

    O1

    C25

    C7

    F4

    C22

    F2

    C24

    Sb1

    C23

    C11

    F5

    C12

    C16

    F1

    F6

    C13

    C15

    C14

    ENDIAMINE LIGANDS

    A. Frstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. Int. Ed. 2008, 47, 3210

  • UPREGULATION OF THE ACCEPTOR PROPERTIES OF NHCS

    A. F. with M. Alcarazo, T,. Stork, A,. Anoop, W. Thiel, Angew. Chem. Int. Ed. 2010, 49, 2542;

    for the cyclophanic NHCs see: A. F. with M. Alcarazo, H. Krause, C. W. Lehmann, J. Am. Chem. Soc. 2007, 129, 12676

  • N NO

    N

    CN

    O

    NMe2O

    N

    CNmCPBA Me2NC(O)Cl

    TMSCN

    76% 54%

    A. Pfaltz, F. Vgtle et al.

    Synthesis 1999, 597

    CYCLOPHANIC NHCS

    A. F. with M. Alcarazo, H. Krause, C. W. Lehmann, J. Am. Chem. Soc. 2007, 129, 12676

  • 1980 cm-1

    NN MesMes

    NN PhPh

    N N

    N

    Ph

    Ph

    PhN

    MeN

    Me

    19902000

    CYCLOPHANIC NHCS

    J. Am. Chem. Soc. 2007, 129, 12676

  • Stable carbenes other than NHCs:

    AMINO-YLID CARBENES (AYCs)

  • AMINO-YLID CARBENES (AYCs)

    A. F. with M. Alcarazo, K. Radkowski, C. W. Lehmann, Angew. Chem. Int. Ed. 2008, 47, 8302

  • C8

    C2N1

    C18B

    C3C18A

    C11C1

    C17

    C4

    C12

    Rh1

    C16

    C13B

    C5

    C13A

    C6

    I1

    N2

    C15

    C14

    C7

    CARBENES STABILIZED BY LATERAL ENAMINES

    A. F. with M. Alcarazo, K. Radkowski, R. Goddard, Chem. Commun. 2011, 776

  • C24

    C34

    C35

    C25

    C23

    C36C33

    C26

    C22

    C32

    C21

    C31

    P1

    C14

    C1

    C3

    C13

    C12

    C2

    Au1

    C4

    C41 C8

    C7

    C11

    C5

    C6

    C9

    C10

    Cl1

    C42

    C46C43

    C45

    C44A. F. with M. Alcarazo, R. M. Suarez, R. Goddard,

    Chem. Eur. J. 2010, 16, 9746

    PUSH-PULL HETEROCUMULENES HAVE CARBENE CHARACTER

  • PREPARATION OF IMIDAZOLIUM SALTS WITH

    PREVIOUSLY INACCESSIBLE PATTERNS

    N NR1 R2

    X

    N NR1 R2

    A

    B

    N NR1

    R2X

    C

    N ZR1

    X

    R2NH2

    Y

    NR1

    O

    O

    R3

    R4

    R3 R4

    R3 R4 R3 R4 R3 R4

    HO

    OR4

    R3

    R1NH2

    F

    HX

    E (Z = O)

    D (Z = NR2)

    A. F. with M. Alcarazo, V. Csar, C. W. Lehmann, Chem. Commun. 2006, 2176

    Org. Synth. 2008, 85, 34

  • PREPARATION OF IMIDAZOLIUM SALTS WITH

    PREVIOUSLY INACCESSIBLE PATTERNS

    N N

    X

    N N

    ClO4

    PhN N

    ClO4

    BF4

    NNPh N N

    ClO4

    75% (X = BF4)

    91% (X = ClO4)

    64% 91%

    59% 88%

    N

    N

    BF4

    OMe

    83%

    NN

    BF4 61%

    N N

    MeO

    BF4

    69%

    O3

    C15

    O4

    O1

    Cl1

    C13

    C14

    C6

    O2

    C5

    C7

    C24

    C4C1

    C8

    C21

    C20

    N1

    C9

    N2C16

    C19

    C23

    C2

    C12

    C3

    C17C18

    C10

    C22 C11

    A. Frstner, M. Alcarazo, V. Csar, C. W.

    Lehmann, Chem. Commun. 2006, 2176

  • METAL-NHC COMPLEXES BY OXIDATIVE ADDITION

    N N

    Cl X

    N N

    Pd ClPh3P

    XPd(PPh3)4

    2 PPh3

    1 a-ccis-2a-c

    PPh3

    N N

    Pd PPh3Ph3P

    X

    trans-2a-c

    Cl

    C62

    C4

    C61

    C41

    N2 C42

    C3

    P2

    C1

    C52

    C12

    Pd1

    C2

    C51

    C31

    Cl1

    N1

    C32

    C11

    P1

    C5

    Cl2-

    A. Frstner et al., Organometallics 2003, 22, 907; Chem. Eur. J. 2005, 11, 1833

  • METAL-NHC COMPLEXES BY OXIDATIVE ADDITION

    Pd

    N SPh

    Ph3P PPh3

    Cl

    PF6N N

    NiEt3P PEt3

    Cl

    PF6 PF6N N

    NiPh3P PPh3

    Cl

    Cl

    N N

    Pd PPh3Ph3P

    Cl

    Ph

    C13C14

    C34

    C35

    C15C12

    C55

    C33

    C36

    C54

    C56

    C16C11

    C32

    C31

    C53

    C51C3

    C4

    N2

    C2

    C22

    C52

    P1N5 C1

    C21

    C23C5

    C46C41

    Pd1

    C45

    C26

    C24

    C42

    C25

    C44C43

    Cl2Cl1

    C15

    Cl1

    Cl2

    C14

    C16

    C45C44

    C46

    Pd1

    C13

    C11

    C43

    C41

    C12

    C42

    O5

    C4

    P1

    N2

    C1

    C36

    C31

    C3

    C35

    C21

    C26

    C32

    C34

    C22

    C33

    C25

    C23

    C24

    D. Kremzow, G. Seidel, C. W. Lehmann, A. Frstner, Chem. Eur. J. 2005, 11, 1833

  • NEW APPLICATIONS OF

    N-HETEROCYCLIC CARBENE COMPLEXES

    9-R-9-BBN, KOMeR

    OMe

    MeOCl

    OMe

    MeO

    cat.

    Pd(OAc)2 cat.

    ClN N

    R = alkyl, allyl, alkynyl, cyclopropyl

    A. Frstner, A. Leitner, Synlett 2001, 290

  • NEW APPLICATIONS OF

    N-HETEROCYCLIC CARBENE COMPLEXES

    CN, NO2, CF3 etc.

    X = C(O)R, COOR, CHO

    ClX

    O

    B

    OO

    B

    O

    N NCl

    cat.

    Pd(OAc)2 cat, KOAc, THF O

    B

    O

    X

    1

    2

    A. Frstner, G. Seidel, Org. Lett. 2002, 4, 541

  • anti : syn = 97 : 371%

    N NCl

    cat.+ PhB(OH)2

    RhCl3.3H20 cat.

    CHO

    NO

    Boc NO

    Boc

    OH

    NEW APPLICATIONS OF

    N-HETEROCYCLIC CARBENE COMPLEXES

    A. Frstner, H. Krause, Adv. Synth. Catal. 2001, 343, 343

  • NHCs CAN COEXIST WITH OLEFINIC SITES

    Br

    NN

    NN

    Ru

    PCy3

    Cl

    Cl

    PhRu

    PCy3

    Cl

    Cl

    NN

    [a]

    [b] [c]

    2 3

    4 5

    Mes MesN N

    Mes Mes

    C21

    C13 C12C22

    C14

    C3

    C11

    C4N2

    C8

    C7

    C15

    N5

    C16

    C1 C6

    C9

    C23

    C10

    A. Frstner, H. Krause, L. Ackermann, C. W. Lehmann, Chem. Commun. 2001, 2240

  • FIRST EXAMPLE OF A METAL-SILYLENE COMPLEX

    USED AS A CATALYST

    N

    Si

    NCl

    Cl N

    Si

    NC8K

    67%Pd(PPh3)4

    50%

    Pd

    Si

    Pd

    Si

    PPh3Ph3P

    tBu tBuN N

    tBu tBuNN

    O

    88%

    B(OH)2

    +

    O

    Br

    5 mol%

    DME, K2CO3, 80C

    A. Frstner, H. Krause, C. W. Lehmann, Chem. Commun. 2001, 2372

    C22*

    C21*

    C4*

    C8

    C11*

    C9

    P1*

    C3*

    C7

    C5*

    C12*

    C31*

    C32*

    N1*

    N2

    Pd1*

    C1*

    C2

    Si1

    Si1*

    C2*

    C1

    Pd1

    N2*

    N1

    C32

    C31

    C12

    C5

    C7*

    C3

    P1

    C9*

    C11

    C8*

    C4

    C21

    C22