Monodentate Transient Directing Group Assisted Pd-Catalyzed Direct Dehydrogenative Cross-Coupling of Benzaldehydes with Arenes toward 9-Fluorenones.
Wang, Yi-Feng; Xu, Wen-Gang; Sun, Bing; Yu, Qin-Qin; Li, Tuan-Jie; Zhang, Fang-Lin; The Journal of organic chemistry 84 (2019) 13104–13111; doi:10.1021/acs.joc.9b02139

data_4034099
_publ_section_title
;
 Monodentate Transient Directing Group Assisted Pd-Catalyzed Direct
 Dehydrogenative Cross-Coupling of Benzaldehydes with Arenes toward
 9-Fluorenones.
;
_journal_issue                   20
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13104
_journal_page_last               13111
_journal_paper_doi               10.1021/acs.joc.9b02139
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H10 Cl2 O'
_chemical_formula_sum            'C19 H10 Cl2 O'
_chemical_formula_weight         325.17
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-07-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.07810(10)
_cell_length_b                   7.48190(10)
_cell_length_c                   27.9855(3)
_cell_measurement_reflns_used    16075
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.3790
_cell_measurement_theta_min      3.1560
_cell_volume                     1482.05(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -115.00 -80.00   0.50    0.05    --  -43.30 -77.00-150.00   70
  2  \w   -118.00 -67.00   0.50    0.05    --  -43.30 -49.00 -41.00  102
  3  \w    -60.00 -30.00   0.50    0.05    --  -43.30 -49.00 -41.00   60
  4  \w    -54.00 -21.00   0.50    0.05    --  -43.30 -37.00 -30.00   66
  5  \w    -62.00 -14.00   0.50    0.05    --  -43.30 -77.00 -30.00   96
  6  \w    -39.00 -14.00   0.50    0.05    --  -43.30 -77.00  30.00   50
  7  \w    -96.00 -20.00   0.50    0.05    --  -43.30 -57.00  60.00  152
  8  \w   -116.00 -78.00   0.50    0.05    --  -43.30 -77.00  30.00   76
  9  \w   -116.00 -80.00   0.50    0.05    --  -43.30 -77.00 -90.00   72
 10  \w    -76.00 -19.00   0.50    0.05    --  -43.30 -77.00 -90.00  114
 11  \w    -48.00 -18.00   0.50    0.05    --  -43.30 -77.00-150.00   60
 12  \w    -87.00 -61.00   0.50    0.22    --  -90.25 -77.00 -90.00   52
 13  \w    -94.00 -64.00   0.50    0.22    --  -90.25 -70.00-149.43   60
 14  \w   -141.00-116.00   0.50    0.22    --  -90.25 -49.00 -41.00   50
 15  \w   -144.00-115.00   0.50    0.22    --  -90.25 -77.00   0.00   58
 16  \w   -140.00-104.00   0.50    0.22    --  -90.25 -74.00  36.15   72
 17  \w    -95.00 -61.00   0.50    0.22    --  -90.25 -77.00   0.00   68
 18  \w    -89.00 -63.00   0.50    0.22    --  -90.25 -73.00 -32.02   52
 19  \w    -99.00 -61.00   0.50    0.22    --  -90.25 -78.00-107.86   76
 20  \w    -87.00 -61.00   0.50    0.22    --  -90.25 -77.00-150.00   52
 21  \w   -105.00 -61.00   0.50    0.22    --  -90.25 -77.00 -99.54   88
 22  \w   -148.00-113.00   0.50    0.22    --  -90.25 -78.00-107.86   70
 23  \w   -108.00 -61.00   0.50    0.22    --  -90.25 -77.00-120.00   94
 24  \w    -89.00 -63.00   0.50    0.22    --  -90.25 -73.00   7.29   52
 25  \w    -93.00 -64.00   0.50    0.22    --  -90.25 -72.00 -22.19   58
 26  \w    -87.00 -61.00   0.50    0.22    --  -90.25 -77.00  30.00   52
 27  \w    -90.00 -64.00   0.50    0.22    --  -90.25 -70.00  58.52   52
 28  \w    -88.00 -61.00   0.50    0.22    --  -90.25 -77.00 120.00   54
 29  \w   -112.00 -65.00   0.50    0.22    --  -90.25 -77.00 150.00   94
 30  \w   -152.00-126.00   0.50    0.22    --  -90.25 -77.00 120.00   52
 31  \w    -91.00 -63.00   0.50    0.22    --  -90.25 -72.00 176.66   56
 32  \w   -164.00-138.00   0.50    0.22    --  -90.25 -72.00 -22.19   52
 33  \w    -90.00 -64.00   0.50    0.22    --  -90.25 -72.00  92.80   52
 34  \w    -93.00 -62.00   0.50    0.22    --  -90.25 -74.00  36.15   62
 35  \w    -87.00 -62.00   0.50    0.22    --  -90.25 -76.00 -75.29   50
 36  \w    -90.00 -61.00   0.50    0.22    --  -90.25 -77.00 -60.00   58
 37  \w   -100.00 -65.00   0.50    0.22    --  -90.25 -69.00-171.57   70
 38  \w   -151.00-125.00   0.50    0.22    --  -90.25 -77.00 -90.00   52
 39  \w    -91.00 -16.00   0.50    0.22    --  -90.25 125.00 150.00  150
 40  \w     82.00 177.00   0.50    0.22    --  109.88  77.00-180.00  190
 41  \w     82.00 178.00   0.50    0.22    --  109.88  77.00-120.00  192
 42  \w     98.00 150.00   0.50    0.22    --  109.88  77.00 -90.00  104
 43  \w     89.00 164.00   0.50    0.22    --  109.88  61.00 -30.00  150
 44  \w     86.00 177.00   0.50    0.22    --  109.88  77.00  30.00  182
 45  \w     98.00 178.00   0.50    0.22    --  109.88  49.00 106.00  160
 46  \w     93.00 177.00   0.50    0.22    --  109.88  61.00 120.00  168
 47  \w     97.00 169.00   0.50    0.22    --  109.88  45.00 150.00  144
 48  \w     15.00  67.00   0.50    0.05    --   43.30  77.00 120.00  104
 49  \w     21.00  60.00   0.50    0.05    --   43.30  49.00 106.00   78
 50  \w     72.00 118.00   0.50    0.05    --   43.30  49.00 106.00   92
 51  \w     46.00  96.00   0.50    0.22    --  109.88 -49.00 -41.00  100
 52  \w     31.00  62.00   0.50    0.22    --  109.88 -30.00 120.00   62
 53  \w     84.00 120.00   0.50    0.22    --  109.88 -30.00 120.00   72
 54  \w     23.00  66.00   0.50    0.05    --   43.30 -49.00 -41.00   86
 55  \w    -31.00  10.00   0.50    0.05    --   43.30 -49.00 -41.00   82
 56  \w    -49.00  31.00   0.50    0.05    --  -43.30  49.00 106.00  160
 57  \w    -73.00 -48.00   0.50    0.22    --  -90.25  49.00 106.00   50
 58  \w     14.00  50.00   0.50    0.05    --   43.30  77.00-150.00   72
 59  \w     36.00 108.00   0.50    0.22    --  109.88 -94.00   0.00  144
 60  \w     37.00 121.00   0.50    0.22    --  109.88-125.00 -30.00  168
 61  \w     70.00 108.00   0.50    0.22    --  109.88 -94.00 120.00   76
 62  \w     37.00 108.00   0.50    0.22    --  109.88 -94.00  60.00  142
 63  \w     48.00 105.00   0.50    0.22    --  109.88 -94.00 -60.00  114
 64  \w     38.00 112.00   0.50    0.22    --  109.88-125.00-180.00  148
 65  \w     71.00  98.00   0.50    0.22    --  109.88 -94.00-150.00   54
 66  \w     39.00  65.00   0.50    0.22    --  109.88 -94.00-150.00   52
 67  \w     31.00  97.00   0.50    0.05    --   43.30-125.00 -30.00  132
 68  \w    -96.00 -59.00   0.50    0.22    --  -90.25 -81.00 -36.19   74
 69  \w   -114.00 -88.00   0.50    0.05    --  -43.30-125.00-120.00   52
 70  \w    -84.00 -59.00   0.50    0.22    --  -90.25 -81.00  63.15   50
 71  \w   -126.00 -59.00   0.50    0.22    --  -90.25 -81.00  93.00  134
 72  \w   -150.00-125.00   0.50    0.22    --  -90.25 -81.00  63.15   50
 73  \w   -155.00-130.00   0.50    0.22    --  -90.25 -81.00  93.00   50
 74  \w    -84.00 -59.00   0.50    0.22    --  -90.25 -82.00 169.79   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1761440000
_diffrn_orient_matrix_UB_12      0.0621196000
_diffrn_orient_matrix_UB_13      -0.0277574000
_diffrn_orient_matrix_UB_21      -0.1091983000
_diffrn_orient_matrix_UB_22      0.1649608000
_diffrn_orient_matrix_UB_23      -0.0179284000
_diffrn_orient_matrix_UB_31      0.0665538000
_diffrn_orient_matrix_UB_32      0.1064373000
_diffrn_orient_matrix_UB_33      0.0440188000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0500
_diffrn_reflns_av_unetI/netI     0.0246
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            28226
_diffrn_reflns_theta_full        75.97
_diffrn_reflns_theta_max         75.97
_diffrn_reflns_theta_min         3.16
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.913
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42501
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.457
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             664
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.133
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.004(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         3025
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0280
_refine_ls_R_factor_gt           0.0273
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0433P)^2^+0.2077P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0737
_refine_ls_wR_factor_ref         0.0745
_reflns_number_gt                2969
_reflns_number_total             3025
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo9b02139_si_003.cif
_cod_data_source_block           exp_3033
_cod_database_code               4034099
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C11(H11), C15(H15), C13(H13), C7(H7), C12(H12), C19(H19), C18(H18),
 C16(H16), C17(H17)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.650
_oxdiff_exptl_absorpt_empirical_full_min 0.606