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_7246957
_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         'C21 H18 O2'
_chemical_formula_sum            'C21 H18 O2'
_chemical_formula_weight         302.35
_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             2022-09-01
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.06.10 svn.r3fa896fb for OlexSys, GUI svn.r6535)
;
_audit_update_record
;
2022-09-01 deposited with the CCDC.	2023-06-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.529(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.6458(2)
_cell_length_b                   6.14330(10)
_cell_length_c                   66.279(2)
_cell_measurement_reflns_used    10642
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.4320
_cell_measurement_theta_min      3.9470
_cell_volume                     3112.05(13)
_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 0.999
_diffrn_measured_fraction_theta_max 0.985
_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     39.00 121.08   0.38    0.26    --   45.09  19.00  90.00  216
  2  \w    104.00 130.98   0.38    1.05    --  109.75  15.00 150.00   71
  3  \w    104.00 130.98   0.38    1.05    --  109.75  15.00 120.00   71
  4  \w    104.00 130.98   0.38    1.05    --  109.75  15.00  60.00   71
  5  \w    104.00 130.98   0.38    1.05    --  109.75  15.00  30.00   71
  6  \w    104.00 130.98   0.38    1.05    --  109.75  15.00   0.00   71
  7  \w     37.00  70.06   0.38    1.05    --  109.75 -77.00  90.00   87
  8  \w     37.00  91.72   0.38    1.05    --  109.75 -95.00  90.00  144
  9  \w    -30.00  14.08   0.38    0.26    --   45.09 -38.00 150.00  116
 10  \w    -30.00  14.08   0.38    0.26    --   45.09 -38.00 120.00  116
 11  \w    -30.00  14.08   0.38    0.26    --   45.09 -38.00  90.00  116
 12  \w     37.00  70.06   0.38    1.05    --  109.75 -77.00-120.00   87
 13  \w    -30.00  14.08   0.38    0.26    --   45.09 -38.00-120.00  116
 14  \w   -117.00 -36.82   0.38    0.26    --  -45.09 -50.00-179.15  211
 15  \w    -62.00 -33.88   0.38    0.26    --  -45.09 -59.00-140.84   74
 16  \w    -62.00 -33.88   0.38    0.26    --  -45.09 -58.00 -79.36   74
 17  \w    -62.00 -32.74   0.38    0.26    --  -45.09 -61.00  87.48   77
 18  \w    -62.00 -34.64   0.38    0.26    --  -45.09 -56.00 120.36   72
 19  \w    -93.00 -23.84   0.38    1.05    --  -97.00  93.00  64.16  182
 20  \w   -100.00 -26.66   0.38    1.05    --  -97.00 125.00   0.00  193
 21  \w    -93.00 -26.12   0.38    1.05    --  -97.00  97.00   4.80  176
 22  \w    -93.00 -26.12   0.38    1.05    --  -97.00 104.00  92.08  176
 23  \w    -49.00  27.00   0.38    0.26    --  -45.09  57.00 120.00  200
 24  \w    -55.00 -23.84   0.38    1.05    --  -97.00  61.00 150.00   82
 25  \w    -55.00 -23.84   0.38    1.05    --  -97.00  61.00   0.00   82
 26  \w    -79.00 -24.28   0.38    1.05    --  -97.00  77.00 -60.00  144
 27  \w    -55.00 -29.92   0.38    1.05    --  -97.00  61.00-120.00   66
 28  \w    -55.00 -23.84   0.38    1.05    --  -97.00  61.00-150.00   82
 29  \w   -140.00 -90.98   0.38    1.05    --  -97.00 -15.00-150.00  129
 30  \w   -140.00 -90.98   0.38    1.05    --  -97.00 -15.00-180.00  129
 31  \w   -170.00-106.92   0.38    1.05    --  -97.00 -77.00-150.00  166
 32  \w   -170.00 -90.20   0.38    1.05    --  -97.00 -46.00 -52.95  210
 33  \w   -140.00 -90.98   0.38    1.05    --  -97.00 -15.00  30.00  129
 34  \w   -140.00 -90.98   0.38    1.05    --  -97.00 -15.00  60.00  129
;
_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      -0.2012125000
_diffrn_orient_matrix_UB_12      0.0146443000
_diffrn_orient_matrix_UB_13      -0.0009502000
_diffrn_orient_matrix_UB_21      -0.0015419000
_diffrn_orient_matrix_UB_22      0.0261802000
_diffrn_orient_matrix_UB_23      0.0231205000
_diffrn_orient_matrix_UB_31      0.0120870000
_diffrn_orient_matrix_UB_32      0.2490747000
_diffrn_orient_matrix_UB_33      -0.0023446000
_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  0.1228
_diffrn_reflns_av_unetI/netI     0.0588
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       78
_diffrn_reflns_limit_l_min       -78
_diffrn_reflns_number            30515
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        66.497
_diffrn_reflns_theta_max         66.497
_diffrn_reflns_theta_min         3.335
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.645
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59361
_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    1.291
_exptl_crystal_description       plate
_exptl_crystal_F_000             1280
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.617
_refine_diff_density_min         -0.585
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     418
_refine_ls_number_reflns         5621
_refine_ls_number_restraints     372
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.1323
_refine_ls_R_factor_gt           0.1298
_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^)+(0.1633P)^2^+21.0796P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3480
_refine_ls_wR_factor_ref         0.3493
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5280
_reflns_number_total             5621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc01403g2.cif
_cod_data_source_block           2022acc0020_d1_100k
_cod_depositor_comments
'Adding full bibliography for 7246950--7246958.cif.'
_cod_database_code               7246957
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C12H12O2
_chemical_oxdiff_usercomment     'RAK-479 small vial'
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.830
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.693(4)
 0.307(4)
2. 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
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C108(H10D,H10E), C109(H10F,H10G), C208(H20D,H20E), C209(H20F,H20G)
4.b Aromatic/amide H refined with riding coordinates:
 C103(H103), C104(H104), C106(H106), C107(H107), C111(H111), C112(H112),
 C115(H115), C117(H117), C118(H118), C119(H119), C120(H120), C203(H203),
 C204(H204), C206(H206), C207(H207), C211(H211), C212(H212), C215(H215),
 C217(H217), C218(H218), C219(H219), C220(H220)
4.c Idealised Me refined as rotating group:
 C101(H10A,H10B,H10C), C201(H20A,H20B,H20C)
;
_shelx_res_checksum              52412
_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-479
_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 1.600
_oxdiff_exptl_absorpt_empirical_full_min 0.581