A phosphine free, inorganic base free, one-pot tandem Mizoroki–Heck olefination/direct arylation/hydrogenation sequence, to give multicyclic alkylated heteroarenes
Kehoe, Roberta A.; Light, Mark E.; Jones, David J.; McGlacken, Gerard P.; Green Chemistry 25 (2023) 5654–5660; doi:10.1039/D3GC01403G

data_7246955
_publ_section_title
;
 A phosphine free, inorganic base free, one-pot tandem Mizoroki--Heck
 olefination/direct arylation/hydrogenation sequence, to give multicyclic
 alkylated heteroarenes
;
_journal_issue                   14
_journal_name_full               'Green Chemistry'
_journal_page_first              5654
_journal_page_last               5660
_journal_paper_doi               10.1039/D3GC01403G
_journal_volume                  25
_journal_year                    2023
_chemical_formula_moiety         'C24 H18 F N O'
_chemical_formula_sum            'C24 H18 F N O'
_chemical_formula_weight         355.39
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-07
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.06.10 svn.r3fa896fb for OlexSys, GUI svn.r6535)
;
_audit_update_record
;
2022-10-07 deposited with the CCDC.	2023-06-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.229(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.6809(2)
_cell_length_b                   13.8095(5)
_cell_length_c                   21.8999(9)
_cell_measurement_reflns_used    12241
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.3040
_cell_measurement_theta_min      3.6930
_cell_volume                     1717.66(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.976
_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    -98.00 -25.00   0.50    0.82    --  -45.20 138.00-177.00  146
  2  \w     20.00  98.00   0.50    0.82    --   45.20-138.00 120.00  156
  3  \w     15.00  93.00   0.50    0.82    --   45.20-132.00 -62.00  156
  4  \w   -107.00 -25.00   0.50    3.28    --  -97.00 138.00-177.00  164
  5  \w   -103.00 -25.00   0.50    3.28    --  -97.00 132.00   6.00  156
  6  \w   -164.00 -90.00   0.50    3.28    --  -97.00-132.00 -62.00  148
  7  \w   -160.00 -87.00   0.50    3.28    --  -97.00-138.00 120.00  146
  8  \w     82.00 161.00   0.50    3.28    --  109.75 138.00-177.00  158
  9  \w     85.00 165.00   0.50    3.28    --  109.75 132.00   6.00  160
 10  \w     37.00 107.00   0.50    3.28    --  109.75-138.00 120.00  140
 11  \w    -62.00 -34.00   0.50    0.82    --  -45.20 -55.00 125.87   56
 12  \w    -93.00 -21.00   0.50    0.82    --  -45.20 132.00   6.00  144
 13  \w    -62.00 -33.00   0.50    0.82    --  -45.20 -60.00 -59.83   58
 14  \w   -119.00 -35.00   0.50    0.82    --  -45.20 -54.00-128.94  168
 15  \w    -62.00 -33.00   0.50    0.82    --  -45.20 -60.00 -30.04   58
 16  \w    -23.00  30.00   0.50    0.82    --  -45.20  38.00  30.00  106
 17  \w    -62.00 -33.00   0.50    0.82    --  -45.20 -59.00  96.92   58
 18  \w    -30.00  15.00   0.50    0.82    --   45.20 -38.00  90.00   90
 19  \w    -30.00  15.00   0.50    0.82    --   45.20 -38.00  30.00   90
 20  \w    -30.00  15.00   0.50    0.82    --   45.20 -38.00   0.00   90
 21  \w    -30.00  15.00   0.50    0.82    --   45.20 -38.00  60.00   90
 22  \w    -55.00 -23.00   0.50    3.28    --  -97.00  61.00  30.00   64
 23  \w    -55.00 -23.00   0.50    3.28    --  -97.00  61.00  90.00   64
 24  \w    -55.00 -23.00   0.50    3.28    --  -97.00  61.00-150.00   64
 25  \w    -55.00 -23.00   0.50    3.28    --  -97.00  61.00 150.00   64
 26  \w   -140.00 -90.00   0.50    3.28    --  -97.00 -15.00-180.00  100
 27  \w   -170.00-106.00   0.50    3.28    --  -97.00 -77.00  30.00  128
 28  \w   -140.00 -90.00   0.50    3.28    --  -97.00 -15.00   0.00  100
 29  \w    -55.00 -23.00   0.50    3.28    --  -97.00  61.00 -30.00   64
 30  \w    -93.00 -23.00   0.50    3.28    --  -97.00  93.00  23.27  140
 31  \w    -55.00 -23.00   0.50    3.28    --  -97.00  61.00   0.00   64
 32  \w    -93.00 -23.00   0.50    3.28    --  -97.00  93.00-105.50  140
 33  \w   -140.00 -90.00   0.50    3.28    --  -97.00 -15.00 -60.00  100
 34  \w    -93.00 -25.00   0.50    3.28    --  -97.00  97.00-138.11  136
 35  \w   -170.00-106.00   0.50    3.28    --  -97.00 -77.00-150.00  128
 36  \w    104.00 132.00   0.50    3.28    --  109.75  15.00 150.00   56
 37  \w    104.00 132.00   0.50    3.28    --  109.75  15.00 -30.00   56
 38  \w    104.00 132.00   0.50    3.28    --  109.75  15.00 120.00   56
 39  \w     37.00  93.00   0.50    3.28    --  109.75 -95.00-150.00  112
 40  \w     37.00  93.00   0.50    3.28    --  109.75 -95.00 -60.00  112
 41  \w     37.00  93.00   0.50    3.28    --  109.75 -95.00   0.00  112
 42  \w     37.00  93.00   0.50    3.28    --  109.75 -95.00 150.00  112
 43  \w     37.00  93.00   0.50    3.28    --  109.75 -95.00-180.00  112
 44  \w    104.00 132.00   0.50    3.28    --  109.75  15.00-180.00   56
 45  \w     37.00  93.00   0.50    3.28    --  109.75 -95.00 -30.00  112
 46  \w     39.00 100.00   0.50    3.28    --  109.75-125.00 150.00  122
 47  \w     37.00  93.00   0.50    3.28    --  109.75 -95.00 120.00  112
 48  \w     37.00  71.00   0.50    3.28    --  109.75 -77.00 -90.00   68
 49  \w    104.00 162.00   0.50    3.28    --  109.75  30.00-150.00  116
 50  \w     37.00  93.00   0.50    3.28    --  109.75 -95.00  30.00  112
 51  \w    104.00 132.00   0.50    3.28    --  109.75  15.00 -60.00   56
 52  \w     38.00 103.00   0.50    3.28    --  109.75-132.00 -62.00  130
 53  \w    -62.00 -33.00   0.50    0.82    --  -45.20 -60.00  13.64   58
 54  \w    -62.00 -33.00   0.50    0.82    --  -45.20 -58.00  65.23   58
 55  \w    -62.00 -34.00   0.50    0.82    --  -45.20 -57.00 168.54   56
 56  \w   -118.00 -48.00   0.50    0.82    --  -45.20 -49.00  58.26  140
 57  \w    -62.00 -33.00   0.50    0.82    --  -45.20 -59.00  38.51   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0158251000
_diffrn_orient_matrix_UB_12      0.0983332000
_diffrn_orient_matrix_UB_13      -0.0330821000
_diffrn_orient_matrix_UB_21      -0.0171650000
_diffrn_orient_matrix_UB_22      -0.0526960000
_diffrn_orient_matrix_UB_23      -0.0619740000
_diffrn_orient_matrix_UB_31      -0.2700562000
_diffrn_orient_matrix_UB_32      -0.0023661000
_diffrn_orient_matrix_UB_33      0.0044398000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            3518
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.633
_diffrn_reflns_theta_min         3.784
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.732
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.755
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.374
_exptl_crystal_description       plate
_exptl_crystal_F_000             744
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.670
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.163
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3518
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.1488
_refine_ls_R_factor_gt           0.1448
_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^)+(0.1701P)^2^+12.0581P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4312
_refine_ls_wR_factor_ref         0.4329
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3311
_reflns_number_total             3518
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc01403g2.cif
_cod_data_source_block           2022acc0026_d1_100k
_cod_depositor_comments
'Adding full bibliography for 7246950--7246958.cif.'
_cod_database_code               7246955
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C12 H12 N1 O1 F1'
_chemical_oxdiff_usercomment     RAK-429
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.873
_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.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C10(H10), C13(H13), C14(H14), C17(H17),
 C18(H18), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C)
;
_shelx_res_checksum              30284
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with silicon oil'
_olex2_submission_original_sample_id RAK-429
_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 1.371
_oxdiff_exptl_absorpt_empirical_full_min 0.608