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_7246954
_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         'C19 H15 N O'
_chemical_formula_sum            'C19 H15 N O'
_chemical_formula_weight         273.32
_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                 97.2680(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1980(2)
_cell_length_b                   5.61880(10)
_cell_length_c                   18.6771(3)
_cell_measurement_reflns_used    10038
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.8060
_cell_measurement_theta_min      3.3620
_cell_volume                     1373.91(4)
_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 1.000
_diffrn_measured_fraction_theta_max 0.986
_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    -20.00   5.00   0.50    0.24    --   46.61 -29.00 155.00   50
  2  \w     47.00 103.00   0.50    0.96    --  101.75 -77.00  90.00  112
  3  \w     34.00  70.00   0.50    0.96    --  101.75 -61.00   0.00   72
  4  \w     31.00  64.00   0.50    0.96    --  101.75 -61.00 -90.00   66
  5  \w     29.00  72.00   0.50    0.96    --  101.75 -61.00-150.00   86
  6  \w     89.00 167.00   0.50    0.96    --  101.75  29.00 -43.00  156
  7  \w    125.00 152.00   0.50    0.96    --  101.75  61.00   0.00   54
  8  \w     81.00 107.00   0.50    0.96    --  101.75  77.00  30.00   52
  9  \w     86.00 115.00   0.50    0.96    --  101.75  61.00   0.00   58
 10  \w     90.00 121.00   0.50    0.96    --  101.75  45.00  30.00   62
 11  \w     79.00 104.00   0.50    0.96    --  101.75  77.00  90.00   50
 12  \w     31.00  78.00   0.50    0.24    --   46.61  77.00  30.00   94
 13  \w     24.00  75.00   0.50    0.24    --   46.61  77.00  60.00  102
 14  \w     39.00  80.00   0.50    0.24    --   46.61  57.00   0.00   82
 15  \w     39.00  66.00   0.50    0.24    --   46.61  37.00   0.00   54
 16  \w     56.00 118.00   0.50    0.24    --   46.61  29.00 -43.00  124
 17  \w     37.00 105.00   0.50    0.96    --  101.75-100.00 -89.40  136
 18  \w    -39.00  26.00   0.50    0.24    --  -46.61  37.00  90.00  130
 19  \w     -3.00  23.00   0.50    0.24    --  -46.61  19.00  90.00   52
 20  \w    -31.00  28.00   0.50    0.24    --  -46.61  29.00 -43.00  118
 21  \w   -101.00 -39.00   0.50    0.96    -- -103.00  77.00 -30.00  124
 22  \w    -63.00 -31.00   0.50    0.96    -- -103.00  61.00-120.00   64
 23  \w    -63.00 -37.00   0.50    0.96    -- -103.00  61.00  60.00   52
 24  \w    -58.00 -33.00   0.50    0.96    -- -103.00  61.00  90.00   50
 25  \w    -62.00 -31.00   0.50    0.96    -- -103.00  61.00 150.00   62
 26  \w   -114.00 -51.00   0.50    0.24    --  -46.61 -29.00 155.00  126
 27  \w   -105.00 -80.00   0.50    0.96    -- -103.00 -78.00  46.55   50
 28  \w   -105.00 -80.00   0.50    0.96    -- -103.00 -78.00  21.30   50
 29  \w   -106.00 -80.00   0.50    0.96    -- -103.00 -77.00  30.00   52
 30  \w   -169.00-126.00   0.50    0.96    -- -103.00 -78.00  46.55   86
 31  \w   -172.00-146.00   0.50    0.96    -- -103.00 -78.00  21.30   52
 32  \w   -114.00 -80.00   0.50    0.96    -- -103.00 -77.00  90.00   68
 33  \w   -105.00 -80.00   0.50    0.96    -- -103.00 -77.00 120.00   50
 34  \w   -161.00-135.00   0.50    0.96    -- -103.00 -77.00 120.00   52
 35  \w   -174.00-135.00   0.50    0.96    -- -103.00 -76.00  36.03   78
 36  \w   -106.00 -80.00   0.50    0.96    -- -103.00 -77.00  60.00   52
 37  \w   -106.00 -80.00   0.50    0.96    -- -103.00 -76.00 113.49   52
 38  \w   -111.00 -85.00   0.50    0.96    -- -103.00 -65.00  92.30   52
 39  \w   -113.00 -88.00   0.50    0.96    -- -103.00 -58.00 120.36   50
 40  \w   -113.00 -87.00   0.50    0.96    -- -103.00 -61.00  60.00   52
 41  \w   -112.00 -86.00   0.50    0.96    -- -103.00 -61.00  55.16   52
 42  \w   -107.00 -81.00   0.50    0.96    -- -103.00 -76.00  36.03   52
 43  \w   -117.00 -91.00   0.50    0.96    -- -103.00 -54.00  -1.93   52
 44  \w   -113.00 -87.00   0.50    0.96    -- -103.00 -61.00  30.00   52
 45  \w   -115.00 -89.00   0.50    0.96    -- -103.00 -53.00  36.45   52
 46  \w   -134.00 -90.00   0.50    0.96    -- -103.00 -46.00  34.43   88
 47  \w   -165.00 -88.00   0.50    0.96    -- -103.00 -58.00  61.33  154
 48  \w   -116.00 -90.00   0.50    0.96    -- -103.00 -48.00  90.37   52
 49  \w   -115.00 -89.00   0.50    0.96    -- -103.00 -51.00 102.40   52
 50  \w   -166.00 -92.00   0.50    0.96    -- -103.00 -46.00  76.29  148
 51  \w   -156.00 -91.00   0.50    0.96    -- -103.00 -45.00  90.00  130
 52  \w   -118.00 -92.00   0.50    0.96    -- -103.00 -45.00 120.00   52
 53  \w   -156.00-131.00   0.50    0.96    -- -103.00 -29.00 155.00   50
 54  \w   -174.00-145.00   0.50    0.96    -- -103.00 -45.00 120.00   58
 55  \w   -106.00 -80.00   0.50    0.96    -- -103.00 -81.00  91.09   52
 56  \w   -104.00 -78.00   0.50    0.96    -- -103.00 -84.00 108.14   52
 57  \w   -137.00-107.00   0.50    0.96    -- -103.00-125.00 -90.00   60
 58  \w   -171.00-142.00   0.50    0.96    -- -103.00-125.00 -90.00   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      -0.0576883000
_diffrn_orient_matrix_UB_12      -0.0570386000
_diffrn_orient_matrix_UB_13      -0.0749742000
_diffrn_orient_matrix_UB_21      0.1005489000
_diffrn_orient_matrix_UB_22      -0.0843273000
_diffrn_orient_matrix_UB_23      -0.0255981000
_diffrn_orient_matrix_UB_31      -0.0203465000
_diffrn_orient_matrix_UB_32      -0.2545322000
_diffrn_orient_matrix_UB_33      0.0252459000
_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  0.1188
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            19810
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.889
_diffrn_reflns_theta_min         3.376
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.639
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42170
_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    1.321
_exptl_crystal_description       block
_exptl_crystal_F_000             576
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.308
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         2774
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0607
_refine_ls_R_factor_gt           0.0564
_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^)+(0.1035P)^2^+0.4243P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1520
_refine_ls_wR_factor_ref         0.1564
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2494
_reflns_number_total             2774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc01403g2.cif
_cod_data_source_block           2022acc0025_a1_100k
_cod_depositor_comments
'Adding full bibliography for 7246950--7246958.cif.'
_cod_database_code               7246954
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C12H12 N1O1'
_chemical_oxdiff_usercomment     RAK-443
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.789
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19)
;
_shelx_res_checksum              13471
_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-443
_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 4.909
_oxdiff_exptl_absorpt_empirical_full_min 0.177