Utilizing Native Directing Groups: Mechanistic Understanding of a Direct Arylation Leads to Formation of Tetracyclic Heterocycles via Tandem Intermolecular, Intramolecular C-H Activation.
Wisniewski, Steven R.; Savage, Scott A.; Romero, Evan O.; Eastgate, Martin D.; Tan, Yichen; Simmons, Eric M.; Plata, R. Erik; Sowa, Jr, John R; Blackmond, Donna G.; The Journal of organic chemistry 84 (2019) 7961–7970; doi:10.1021/acs.joc.9b00823

data_4034664
_publ_section_title
;
 Utilizing Native Directing Groups: Mechanistic Understanding of a Direct
 Arylation Leads to Formation of Tetracyclic Heterocycles via Tandem
 Intermolecular, Intramolecular C-H Activation.
;
_journal_issue                   12
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              7961
_journal_page_last               7970
_journal_paper_doi               10.1021/acs.joc.9b00823
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C28 H27 N7 O2 Pd S, C4 H8 O'
_chemical_formula_sum            'C32 H35 N7 O3 Pd S'
_chemical_formula_weight         704.13
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2015-06-09
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 115.560(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.2701(14)
_cell_length_b                   8.2426(6)
_cell_length_c                   20.8740(16)
_cell_measurement_reflns_used    4511
_cell_measurement_temperature    100
_cell_measurement_theta_max      25.883
_cell_measurement_theta_min      2.343
_cell_volume                     2991.1(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.960
_diffrn_measured_fraction_theta_max 0.954
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0650
_diffrn_reflns_Laue_measured_fraction_full 0.960
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            17092
_diffrn_reflns_point_group_measured_fraction_full 0.960
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.122
_diffrn_reflns_theta_min         1.907
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker TXS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.738
_exptl_absorpt_correction_T_max  0.0943
_exptl_absorpt_correction_T_min  0.0601
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1095 before and 0.0493 after correction.
The Ratio of minimum to maximum transmission is 0.6373.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.564
_exptl_crystal_description       blade
_exptl_crystal_F_000             1448
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.021
_refine_diff_density_min         -0.766
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     400
_refine_ls_number_reflns         6309
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0489
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0752P)^2^+1.0266P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1258
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4549
_reflns_number_total             6309
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00823_si_001.cif
_cod_data_source_block           black16_a
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4034664
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.815
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N7(H7)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7A), C8(H8), C9(H9),
 C15(H15), C16(H16), C17(H17), C21(H21), C23(H23), C24(H24)
2.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              25919
_shelx_hkl_checksum              92196
_olex2_submission_special_instructions 'No special instructions were received'