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_7246956
_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         'C22 H21 N O3'
_chemical_formula_sum            'C22 H21 N O3'
_chemical_formula_weight         347.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-09-02
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.06.10 svn.r3fa896fb for OlexSys, GUI svn.r6535)
;
_audit_update_record
;
2022-09-02 deposited with the CCDC.	2023-06-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.665(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.3497(7)
_cell_length_b                   7.1784(2)
_cell_length_c                   12.8947(5)
_cell_measurement_reflns_used    5813
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.0830
_cell_measurement_theta_min      4.6710
_cell_volume                     1740.37(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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_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 0.994
_diffrn_measured_fraction_theta_max 0.951
_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    -57.00 -28.00   0.50    2.00    --  -97.00  77.00-180.00   58
  2  \w    -51.00 -25.00   0.50    2.00    --  -97.00  61.00-180.00   52
  3  \w    -55.00 -29.00   0.50    2.00    --  -97.00  61.00 -90.00   52
  4  \w    -50.00 -23.00   0.50    2.00    --  -97.00  61.00 -60.00   54
  5  \w    -52.00 -23.00   0.50    2.00    --  -97.00  61.00 -30.00   58
  6  \w    -55.00 -29.00   0.50    2.00    --  -97.00  61.00  60.00   52
  7  \w    -55.00 -29.00   0.50    2.00    --  -97.00  61.00  90.00   52
  8  \w    -55.00 -25.00   0.50    2.00    --  -97.00  61.00 120.00   60
  9  \w    -23.00  30.00   0.50    0.81    --  -45.09  38.00 120.00  106
 10  \w   -118.00 -43.00   0.50    0.81    --  -45.09 -12.00 177.00  150
 11  \w   -120.00 -95.00   0.50    2.00    --  -97.00 -12.00 177.00   50
 12  \w   -132.00 -98.00   0.50    2.00    --  -97.00 -15.00-120.00   68
 13  \w    -88.00 -49.00   0.50    0.81    --  -45.09 125.00 -60.00   78
 14  \w     44.00 112.00   0.50    0.81    --   45.09  12.00 -10.00  136
 15  \w    110.00 159.00   0.50    2.00    --  109.75  30.00-150.00   98
 16  \w    104.00 130.00   0.50    2.00    --  109.75  15.00 -60.00   52
 17  \w    105.00 130.00   0.50    2.00    --  109.75  15.00-180.00   50
 18  \w    104.00 131.00   0.50    2.00    --  109.75  15.00 -90.00   54
 19  \w    116.00 162.00   0.50    2.00    --  109.75  30.00 -30.00   92
 20  \w    106.00 132.00   0.50    2.00    --  109.75  15.00  30.00   52
 21  \w    106.00 132.00   0.50    2.00    --  109.75  15.00 150.00   52
 22  \w     69.00  95.00   0.50    2.00    --  109.75-125.00 150.00   52
 23  \w     42.00  96.00   0.50    2.00    --  109.75-125.00  90.00  108
 24  \w     61.00  87.00   0.50    2.00    --  109.75 -95.00 120.00   52
 25  \w     51.00  89.00   0.50    2.00    --  109.75 -95.00 150.00   76
 26  \w     37.00  69.00   0.50    2.00    --  109.75 -77.00  90.00   64
 27  \w     60.00  93.00   0.50    2.00    --  109.75 -95.00  60.00   66
 28  \w    -27.00   3.00   0.50    0.81    --   45.09 -38.00-120.00   60
;
_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      0.0052240000
_diffrn_orient_matrix_UB_12      -0.0043502000
_diffrn_orient_matrix_UB_13      0.1210721000
_diffrn_orient_matrix_UB_21      -0.0803253000
_diffrn_orient_matrix_UB_22      -0.0397840000
_diffrn_orient_matrix_UB_23      -0.0214454000
_diffrn_orient_matrix_UB_31      0.0151069000
_diffrn_orient_matrix_UB_32      -0.2109172000
_diffrn_orient_matrix_UB_33      0.0016037000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0296
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            10678
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.710
_diffrn_reflns_theta_min         4.704
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.707
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.326
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.225
_refine_diff_density_rms         0.056
_refine_ls_extinction_coef       0.0015(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         3488
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0446
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0856P)^2^+0.3722P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1391
_refine_ls_wR_factor_ref         0.1443
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2955
_reflns_number_total             3488
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc01403g2.cif
_cod_data_source_block           2022acc0024_d1_100k
_cod_depositor_comments
'Adding full bibliography for 7246950--7246958.cif.'
_cod_database_code               7246956
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_usercomment     RAK-441
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.920
_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:
 C6(H6A,H6B), C7(H7A,H7B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C13(H13), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C)
;
_shelx_res_checksum              30167
_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-441
_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 2.598
_oxdiff_exptl_absorpt_empirical_full_min 0.756