Cross-Dehydrogenative Couplings between Indoles and β-Keto Esters: Ligand-Assisted Ligand Tautomerization and Dehydrogenation via a Proton-Assisted Electron Transfer to Pd(II).
Leskinen, Mikko V.; Madarász, Adám; Yip, Kai-Tai; Vuorinen, Aini; Pápai, Imre; Neuvonen, Antti J.; Pihko, Petri M.; Journal of the American Chemical Society 136 (2014) 6453–6462; doi:10.1021/ja501681y

data_4121693
_publ_section_title
;
 Cross-Dehydrogenative Couplings between Indoles and \b-Keto Esters:
 Ligand-Assisted Ligand Tautomerization and Dehydrogenation via a
 Proton-Assisted Electron Transfer to Pd(II).
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6453
_journal_page_last               6462
_journal_paper_doi               10.1021/ja501681y
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C31 H36 N O3'
_chemical_formula_sum            'C31 H36 N O3'
_chemical_formula_weight         470.61
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-02-08
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.0015(8)
_cell_length_b                   10.3219(10)
_cell_length_c                   34.795(3)
_cell_measurement_reflns_used    3074
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      76.1340
_cell_measurement_theta_min      4.9470
_cell_volume                     2873.7(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1977
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0485054000
_diffrn_orient_matrix_UB_12      0.0214232000
_diffrn_orient_matrix_UB_13      0.0423684000
_diffrn_orient_matrix_UB_21      0.1788471000
_diffrn_orient_matrix_UB_22      -0.0360266000
_diffrn_orient_matrix_UB_23      0.0124406000
_diffrn_orient_matrix_UB_31      0.0525284000
_diffrn_orient_matrix_UB_32      0.1431987000
_diffrn_orient_matrix_UB_33      -0.0031883000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0638
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            18253
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        77.1716
_diffrn_reflns_theta_max         77.265
_diffrn_reflns_theta_min         4.468
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.542
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81332
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.088
_exptl_crystal_description       needle
_exptl_crystal_F_000             1012
_exptl_crystal_size_max          0.1805
_exptl_crystal_size_mid          0.0911
_exptl_crystal_size_min          0.0189
_refine_diff_density_max         0.694
_refine_diff_density_min         -0.356
_refine_diff_density_rms         0.081
_refine_ls_abs_structure_details
;
 Flack x determined using 1475 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.5(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     479
_refine_ls_number_reflns         5979
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.1308
_refine_ls_R_factor_gt           0.1074
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1540P)^2^+1.9527P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2750
_refine_ls_wR_factor_ref         0.3025
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                4441
_reflns_number_total             5979
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja501681y_si_003.cif
_cod_data_source_block           teg-1-132_op
_cod_depositor_comments
'Adding full bibliography for 4121693--4121694.cif.'
_cod_database_code               4121693
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C31 H37 N O3'
_reflns_odcompleteness_completeness 98.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     77.17
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C25B(0.5) O15(0.5) O18(0.5) C24B(0.5) H24A(0.5) H24B(0.5)
 H24C(0.5) O1A(0.5) C15B(0.5) C30B(0.5) H30B(0.5) C23B(0.5) H23A(0.5) H23B(0.5)
 H23C(0.5) C28B(0.5) H28B(0.5) C16B(0.5) H16B(0.5) C21B(0.5) H21B(0.5)
 C16A(0.5) H16A(0.5) C29B(0.5) H29B(0.5) C21A(0.5) H21A(0.5) C19B(0.5)
 C17B(0.5) H17A(0.5) H17B(0.5) C20B(0.5) H20A(0.5) H20B(0.5) C17A(0.5)
 H17C(0.5) H17D(0.5) C28A(0.5) H28A(0.5) C30A(0.5) H30A(0.5) C26B(0.5)
 H26B(0.5) C31B(0.5) H31A(0.5) H31B(0.5) H31C(0.5) C20A(0.5) H20C(0.5)
 H20D(0.5) O4(0.5) C19A(0.5) H19A(0.5) H19B(0.5) C31A(0.5) H31D(0.5) H31E(0.5)
 H31F(0.5) C18B(0.5) H18B(0.5) C18A(0.5) H18A(0.5) C25A(0.5) C29A(0.5)
 H29A(0.5) C23A(0.5) H23D(0.5) H23E(0.5) H23F(0.5) C24A(0.5) H24D(0.5)
 H24E(0.5) H24F(0.5) C27B(0.5) H27B(0.5) C26A(0.5) H26A(0.5) C27A(0.5)
 H27A(0.5) C15A(0.5)
3.a Ternary CH refined with riding coordinates:
 C14(H14), C10(H10), C16B(H16B), C21B(H21B), C16A(H16A), C21A(H21A),
 C18B(H18B), C18A(H18A)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C11(H11A,H11B), C17B(H17A,H17B), C20B(H20A,H20B), C17A(H17C,
 H17D), C20A(H20C,H20D), C19A(H19A,H19B)
3.c Me refined with riding coordinates:
 C24B(H24A,H24B,H24C), C23B(H23A,H23B,H23C), C31B(H31A,H31B,H31C), C31A(H31D,
 H31E,H31F), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F)
3.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C8(H8), C6(H6), C15(H15), C30B(H30B), C28B(H28B), C29B(H29B),
 C28A(H28A), C30A(H30A), C26B(H26B), C29A(H29A), C27B(H27B), C26A(H26A),
 C27A(H27A)
3.e Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;