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_7246958
_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_absolute_configuration ad
_chemical_formula_moiety         'C23 H23 N O4'
_chemical_formula_sum            'C23 H23 N O4'
_chemical_formula_weight         377.42
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.40640(10)
_cell_length_b                   9.64370(10)
_cell_length_c                   36.2282(5)
_cell_measurement_reflns_used    12143
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.1450
_cell_measurement_theta_min      4.7230
_cell_volume                     1888.86(5)
_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_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 0.972
_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      2.00  80.00   0.50    1.00    --   45.09-111.00 -43.00  156
  2  \w   -171.00 -90.00   0.50    2.00    --  -97.00 -31.00 164.00  162
  3  \w    -92.00 -27.00   0.50    2.00    --  -97.00 111.00  50.00  130
  4  \w     40.00  92.00   0.50    2.00    --  109.75-111.00 -43.00  104
  5  \w    100.00 175.00   0.50    2.00    --  109.75  97.00 151.00  150
  6  \w    -23.00  30.00   0.50    1.00    --  -45.09  38.00   0.00  106
  7  \w    -23.00  30.00   0.50    1.00    --  -45.09  38.00  60.00  106
  8  \w    -31.00   4.00   0.50    1.00    --   45.09 -31.00 164.00   70
  9  \w    -30.00  15.00   0.50    1.00    --   45.09 -38.00  60.00   90
 10  \w    -79.00 -23.00   0.50    2.00    --  -97.00  77.00 150.00  112
 11  \w    -55.00 -23.00   0.50    2.00    --  -97.00  61.00  90.00   64
 12  \w   -170.00-106.00   0.50    2.00    --  -97.00 -95.00 -90.00  128
 13  \w    -55.00 -23.00   0.50    2.00    --  -97.00  61.00  60.00   64
 14  \w    -55.00 -23.00   0.50    2.00    --  -97.00  61.00 -30.00   64
 15  \w    -55.00 -23.00   0.50    2.00    --  -97.00  61.00 150.00   64
 16  \w    104.00 132.00   0.50    2.00    --  109.75  15.00 150.00   56
 17  \w    104.00 132.00   0.50    2.00    --  109.75  15.00 120.00   56
 18  \w     37.00  71.00   0.50    2.00    --  109.75 -77.00  30.00   68
 19  \w    104.00 132.00   0.50    2.00    --  109.75  15.00  90.00   56
 20  \w    104.00 132.00   0.50    2.00    --  109.75  15.00 -90.00   56
 21  \w     39.00 100.00   0.50    2.00    --  109.75-125.00 150.00  122
 22  \w    104.00 132.00   0.50    2.00    --  109.75  15.00 -60.00   56
 23  \w     37.00  71.00   0.50    2.00    --  109.75 -77.00-120.00   68
 24  \w     40.00 121.00   0.50    1.00    --   45.09  31.00 -35.00  162
 25  \w    -30.00  15.00   0.50    1.00    --   45.09 -38.00-150.00   90
 26  \w     39.00 120.00   0.50    1.00    --   45.09  38.00-120.00  162
 27  \w     39.00 120.00   0.50    1.00    --   45.09  38.00  30.00  162
 28  \w     39.00 120.00   0.50    1.00    --   45.09  38.00  90.00  162
 29  \w   -140.00-104.00   0.50    2.00    --  -97.00 -15.00 -30.00   72
;
_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      0.2780730000
_diffrn_orient_matrix_UB_12      0.0280521000
_diffrn_orient_matrix_UB_13      0.0055186000
_diffrn_orient_matrix_UB_21      0.0166241000
_diffrn_orient_matrix_UB_22      0.0576240000
_diffrn_orient_matrix_UB_23      -0.0395939000
_diffrn_orient_matrix_UB_31      -0.0599502000
_diffrn_orient_matrix_UB_32      0.1463000000
_diffrn_orient_matrix_UB_33      0.0145194000
_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  0.0385
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            18320
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.382
_diffrn_reflns_theta_min         4.745
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.735
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66875
_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    1.327
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.135
_refine_diff_density_min         -0.192
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1393 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.16(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         3778
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0311
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0409P)^2^+0.3378P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0739
_refine_ls_wR_factor_ref         0.0751
_reflns_Friedel_coverage         0.666
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.932
_reflns_number_gt                3609
_reflns_number_total             3778
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc01403g2.cif
_cod_data_source_block           2022acc0022_d1_100k
_cod_depositor_comments
'Adding full bibliography for 7246950--7246958.cif.'
_cod_database_code               7246958
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C12H12N2O3
_chemical_oxdiff_usercomment     RAK-439
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.917
_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), C12(H12), C13(H13), C14(H14), C19(H19), C21(H21), C22(H22)
2.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              74180
_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-439
_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 1.814
_oxdiff_exptl_absorpt_empirical_full_min 0.604