1,5-Hydrogen atom transfer of α-iminyl radical cations: a new platform for relay annulation for pyridine derivatives and axially chiral heterobiaryls.
Zhou, Yu-Qiang; He, Kui-Cheng; Zheng, Wei-Hao; Lv, Jing-Fang; He, Shi-Mei; Yu, Ning; Yang, Yun-Bo; Liu, Lv-Yan; Jiang, Kun; Wei, Ye; Chemical science 15 (2024) 7502–7514; doi:10.1039/d4sc01858c

data_1572057
_publ_section_title
;
 1,5-Hydrogen atom transfer of &#x3b1;-iminyl radical cations: a new
 platform for relay annulation for pyridine derivatives and axially chiral
 heterobiaryls.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              7502
_journal_page_last               7514
_journal_paper_doi               10.1039/d4sc01858c
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C30 H29 N O2'
_chemical_formula_sum            'C30 H29 N O2'
_chemical_formula_weight         435.54
_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     direct
_audit_creation_date             2023-05-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-11-09 deposited with the CCDC.	2024-04-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.15719(19)
_cell_length_b                   11.2106(2)
_cell_length_c                   27.1349(6)
_cell_measurement_reflns_used    7509
_cell_measurement_temperature    291.19(10)
_cell_measurement_theta_max      71.4420
_cell_measurement_theta_min      3.9350
_cell_volume                     2481.41(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      291.19(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0243
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.983
_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   -103.00 -19.00   1.00    1.00    --  -35.97 -57.00-120.00   84
  2  \w   -105.00 -17.00   1.00    1.00    --  -35.97 -38.00 -60.00   88
  3  \w     28.00  90.00   1.00    1.00    --   35.97-126.00   0.00   62
  4  \w    -35.00  65.00   1.00    1.00    --   35.97 -19.00 -90.00  100
  5  \w    103.00 176.00   1.00    1.39    --  107.97  77.00-120.00   73
  6  \w    103.00 176.00   1.00    1.39    --  107.97  77.00-180.00   73
  7  \w     39.00 106.00   1.00    1.39    --  107.97 -95.00-120.00   67
  8  \w     40.00 125.00   1.00    1.39    --  107.97 -45.00-120.00   85
  9  \w     38.00 109.00   1.00    1.39    --  107.97-112.00  60.00   71
 10  \w     87.00 178.00   1.00    1.39    --  107.97  30.00  60.00   91
 11  \w   -103.00 -19.00   1.00    1.00    --  -35.97 -57.00  60.00   84
 12  \w   -103.00 -19.00   1.00    1.00    --  -35.97 -57.00 150.00   84
 13  \w    -53.00  31.00   1.00    1.00    --  -35.97  57.00-120.00   84
 14  \w      6.00  75.00   1.00    1.00    --   35.97 -99.00 150.00   69
 15  \w     70.00  95.00   1.00    1.39    --  107.97  15.00 150.00   25
 16  \w     91.00 176.00   1.00    1.39    --  107.97  45.00 -30.00   85
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0004618000
_diffrn_orient_matrix_UB_12      -0.1283914000
_diffrn_orient_matrix_UB_13      0.0201785000
_diffrn_orient_matrix_UB_21      -0.0349503000
_diffrn_orient_matrix_UB_22      -0.0481145000
_diffrn_orient_matrix_UB_23      -0.0521236000
_diffrn_orient_matrix_UB_31      0.1857045000
_diffrn_orient_matrix_UB_32      -0.0087647000
_diffrn_orient_matrix_UB_33      -0.0098516000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            13056
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.727
_diffrn_reflns_theta_min         4.267
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.564
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.02596
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.166
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.31
_refine_diff_density_max         0.188
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 1574 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.13(18)
_refine_ls_extinction_coef       0.0036(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     304
_refine_ls_number_reflns         4632
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0533
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0803P)^2^+0.1720P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1411
_refine_ls_wR_factor_ref         0.1460
_reflns_Friedel_coverage         0.696
_reflns_Friedel_fraction_full    0.961
_reflns_Friedel_fraction_max     0.917
_reflns_number_gt                4280
_reflns_number_total             4632
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01858c2.cif
_cod_data_source_block           zyq-3-crystal
_cod_original_cell_volume        2481.40(9)
_cod_database_code               1572057
_shelxl_version_number           2014-1
_chemical_oxdiff_usercomment     'C1 H1 N1 O1'
_shelx_estimated_absorpt_t_max   0.845
_shelx_estimated_absorpt_t_min   0.814
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C14(H14), C18(H18), C19(H19),
 C20(H20), C21(H21), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C)
;
_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 27.136
_oxdiff_exptl_absorpt_empirical_full_min 0.372