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_4034100
_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_formula_moiety         'C49 H34 N2 O'
_chemical_formula_sum            'C49 H34 N2 O'
_chemical_formula_weight         666.78
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-20
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.01.05 svn.r3372 for Rigaku Oxford Diffraction, GUI svn.r5289)
;
_cell_angle_alpha                103.5340(10)
_cell_angle_beta                 99.8190(10)
_cell_angle_gamma                102.0300(10)
_cell_formula_units_Z            2
_cell_length_a                   7.34570(10)
_cell_length_b                   14.90980(10)
_cell_length_c                   17.6269(2)
_cell_measurement_reflns_used    20288
_cell_measurement_temperature    293
_cell_measurement_theta_max      75.5350
_cell_measurement_theta_min      2.6490
_cell_volume                     1786.23(4)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     24.00  56.00   0.50    0.97    --   43.30  37.00  30.00   64
  2  \w     63.00 121.00   0.50    0.97    --   43.30  37.00  30.00  116
  3  \w     88.00 127.00   0.50    3.87    --  109.88 133.00 135.00   78
  4  \w    141.00 178.00   0.50    3.87    --  109.88  77.00 120.00   74
  5  \w    107.00 132.00   0.50    3.87    --  109.88 136.00 -46.00   50
  6  \w     92.00 156.00   0.50    3.87    --  109.88 125.00 -90.00  128
  7  \w    103.00 177.00   0.50    3.87    --  109.88  61.00-120.00  148
  8  \w    142.00 177.00   0.50    3.87    --  109.88  45.00 -60.00   70
  9  \w    128.00 177.00   0.50    3.87    --  109.88  61.00-180.00   98
 10  \w     91.00 176.00   0.50    3.87    --  109.88  61.00   0.00  170
 11  \w     82.00 118.00   0.50    3.87    --  109.88  77.00 120.00   72
 12  \w     89.00 177.00   0.50    3.87    --  109.88  61.00  60.00  176
 13  \w    100.00 127.00   0.50    3.87    --  109.88 -61.00  30.00   54
 14  \w     63.00 123.00   0.50    3.87    --  109.88-133.00  66.00  120
 15  \w     53.00  86.00   0.50    3.87    --  109.88 -94.00  90.00   66
 16  \w     46.00 108.00   0.50    3.87    --  109.88 -94.00 120.00  124
 17  \w     36.00  84.00   0.50    0.97    --   43.30-133.00  66.00   96
 18  \w     37.00  87.00   0.50    3.87    --  109.88 -61.00  30.00  100
 19  \w     38.00  86.00   0.50    0.97    --   43.30-136.00-110.00   96
 20  \w     38.00 124.00   0.50    3.87    --  109.88-136.00-110.00  172
 21  \w     40.00 107.00   0.50    3.87    --  109.88 -94.00 -90.00  134
 22  \w     40.00 131.00   0.50    3.87    --  109.88 -61.00-150.00  182
 23  \w     89.00 138.00   0.50    3.87    --  109.88  45.00 -60.00   98
 24  \w     88.00 173.00   0.50    3.87    --  109.88  61.00-150.00  170
 25  \w     89.00 118.00   0.50    3.87    --  109.88  61.00-180.00   58
 26  \w     22.00  47.00   0.50    0.97    --   43.30  57.00  90.00   50
 27  \w     90.00 166.00   0.50    3.87    --  109.88  45.00 120.00  152
 28  \w    -54.00 -14.00   0.50    0.97    --  -43.30 -77.00-150.00   80
 29  \w    -68.00 -14.00   0.50    0.97    --  -43.30 -77.00 -90.00  108
 30  \w    -63.00 -20.00   0.50    0.97    --  -43.30 -57.00   0.00   86
 31  \w    -76.00 -16.00   0.50    0.97    --  -43.30 -77.00  60.00  120
 32  \w    -74.00 -14.00   0.50    0.97    --  -43.30 -77.00 120.00  120
 33  \w    -96.00 -61.00   0.50    3.87    --  -90.25 -77.00 130.28   70
 34  \w    -92.00 -60.00   0.50    3.87    --  -90.25 -80.00 171.34   64
 35  \w    -91.00 -61.00   0.50    3.87    --  -90.25 -77.00 120.00   60
 36  \w    -92.00 -61.00   0.50    3.87    --  -90.25 -77.00 150.00   62
 37  \w    -93.00 -62.00   0.50    3.87    --  -90.25 -74.00 138.92   62
 38  \w    -97.00 -61.00   0.50    3.87    --  -90.25 -77.00  60.00   72
 39  \w    -92.00 -62.00   0.50    3.87    --  -90.25 -75.00  33.13   60
 40  \w    -90.00 -59.00   0.50    3.87    --  -90.25 -83.00  29.05   62
 41  \w   -103.00 -64.00   0.50    3.87    --  -90.25 -69.00  34.91   78
 42  \w    -92.00 -66.00   0.50    3.87    --  -90.25 -65.00 -28.78   52
 43  \w    -94.00 -62.00   0.50    3.87    --  -90.25 -75.00 -86.10   64
 44  \w    -91.00 -61.00   0.50    3.87    --  -90.25 -78.00-129.95   60
 45  \w    -91.00 -61.00   0.50    3.87    --  -90.25 -77.00-150.00   60
 46  \w    -88.00 -62.00   0.50    3.87    --  -90.25 -75.00-103.60   52
 47  \w    -93.00 -60.00   0.50    3.87    --  -90.25 -82.00-156.49   66
 48  \w    -98.00 -61.00   0.50    3.87    --  -90.25 -77.00-120.00   74
 49  \w    -93.00 -65.00   0.50    3.87    --  -90.25 -67.00 -87.31   56
 50  \w   -100.00 -61.00   0.50    3.87    --  -90.25 -77.00   0.00   78
 51  \w   -115.00 -90.00   0.50    0.97    --  -43.30-133.00  66.00   50
 52  \w   -114.00 -84.00   0.50    0.97    --  -43.30 -77.00  60.00   60
 53  \w   -114.00 -88.00   0.50    0.97    --  -43.30 -77.00 120.00   52
 54  \w   -116.00 -23.00   0.50    0.97    --  -43.30 -57.00 150.00  186
 55  \w    -98.00 -61.00   0.50    3.87    --  -90.25 -77.00 104.01   74
 56  \w    -95.00 -61.00   0.50    3.87    --  -90.25 -77.00  90.00   68
 57  \w   -108.00 -82.00   0.50    0.97    --  -43.30 -57.00   0.00   52
 58  \w   -100.00 -14.00   0.50    0.97    --  -43.30 -77.00 -30.00  172
 59  \w    -96.00 -61.00   0.50    3.87    --  -90.25 -77.00-180.00   70
 60  \w   -113.00 -88.00   0.50    0.97    --  -43.30-136.00-110.00   50
 61  \w   -108.00 -82.00   0.50    0.97    --  -43.30 -77.00 -90.00   52
 62  \w   -114.00 -89.00   0.50    3.87    --  -90.25-136.00-110.00   50
 63  \w   -120.00 -60.00   0.50    3.87    --  -90.25 -79.00 -37.35  120
 64  \w   -115.00 -62.00   0.50    3.87    --  -90.25 -75.00  77.57  106
 65  \w   -127.00 -61.00   0.50    3.87    --  -90.25 -77.00 -30.00  132
 66  \w   -130.00 -61.00   0.50    3.87    --  -90.25 -77.00 -60.00  138
 67  \w   -115.00 -17.00   0.50    0.97    --  -43.30 -19.00-180.00  196
 68  \w   -100.00 -49.00   0.50    0.97    --  -43.30 136.00 -46.00  102
 69  \w    -96.00 -43.00   0.50    0.97    --  -43.30 133.00 135.00  106
 70  \w    -92.00 -48.00   0.50    3.87    --  -90.25 133.00 135.00   88
 71  \w   -160.00-135.00   0.50    3.87    --  -90.25 -74.00 138.92   50
 72  \w   -163.00-125.00   0.50    3.87    --  -90.25 -80.00 171.34   76
 73  \w   -164.00-106.00   0.50    3.87    --  -90.25 -77.00 120.00  116
 74  \w   -139.00-114.00   0.50    3.87    --  -90.25-133.00  66.00   50
 75  \w   -154.00-128.00   0.50    3.87    --  -90.25 -75.00  77.57   52
 76  \w   -154.00-128.00   0.50    3.87    --  -90.25 -83.00  29.05   52
 77  \w   -124.00 -99.00   0.50    3.87    --  -90.25 -83.00  29.05   50
 78  \w   -145.00-117.00   0.50    3.87    --  -90.25 -75.00 -86.10   56
 79  \w   -153.00-111.00   0.50    3.87    --  -90.25 -82.00-156.49   84
 80  \w   -140.00-115.00   0.50    3.87    --  -90.25 -77.00-180.00   50
 81  \w   -153.00-128.00   0.50    3.87    --  -90.25 -75.00-103.60   50
 82  \w   -161.00-136.00   0.50    3.87    --  -90.25 -77.00 -30.00   50
 83  \w   -144.00-118.00   0.50    3.87    --  -90.25 -77.00  90.00   52
;
_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      -0.1232137000
_diffrn_orient_matrix_UB_12      -0.1033279000
_diffrn_orient_matrix_UB_13      -0.0198775000
_diffrn_orient_matrix_UB_21      0.0241469000
_diffrn_orient_matrix_UB_22      0.0089058000
_diffrn_orient_matrix_UB_23      0.0902207000
_diffrn_orient_matrix_UB_31      -0.1811079000
_diffrn_orient_matrix_UB_32      0.0367758000
_diffrn_orient_matrix_UB_33      -0.0003753000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            40319
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         2.650
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.569
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39773
_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            'reddish red'
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.240
_exptl_crystal_description       needle
_exptl_crystal_F_000             700
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         6384
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0518
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0660P)^2^+0.6320P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1447
_refine_ls_wR_factor_ref         0.1505
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5616
_reflns_number_total             6384
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b02139_si_004.cif
_cod_data_source_block           cjm-wyf-hong
_cod_database_code               4034100
_shelx_shelxl_version_number     2018/1
_diffrn_oxdiff_ac3_digest_frames
;
01e37c5fc3c4d9b5a4422350fa4fe1741e07294ea6d
;
_diffrn_oxdiff_ac3_digest_hkl
;
016fdc2506c20a7e59579737c2b99ba211957f
;
_reflns_odcompleteness_completeness 99.89
_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:
 C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H), C00L(H00L), C00M(H00M),
 C00N(H00N), C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00T(H00T),
 C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z),
 C010(H010), C011(H011), C013(H013), C014(H014), C015(H015), C016(H016),
 C017(H017), C018(H018), C019(H019), C01A(H01A), C01B(H01B), C01C(H01C),
 C01D(H01D), C01E(H01E), C01F(H01F), C01G(H01G)
;
_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 1.533
_oxdiff_exptl_absorpt_empirical_full_min 0.332