Synthesis of carbinoxamine via α-C(sp3)–H 2-pyridylation of O, S or N-containing compounds enabled by non-D–A-type super organoreductants and sulfoxide- or sulfide HAT reagents
Cui, Xian-Chao; Zhang, Hu; Wang, Yi-Ping; Qu, Jian-Ping; Kang, Yan-Biao; Chemical Science 13 (2022) 11246–11251; doi:10.1039/D2SC03504A

data_1567653
_publ_section_title
;
 Synthesis of carbinoxamine via \a-C(sp3)--H 2-pyridylation of O, S or
 N-containing compounds enabled by non-D--A-type super organoreductants
 and sulfoxide- or sulfide HAT reagents
;
_journal_issue                   37
_journal_name_full               'Chemical Science'
_journal_page_first              11246
_journal_page_last               11251
_journal_paper_doi               10.1039/D2SC03504A
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C27 H26 N2 O'
_chemical_formula_sum            'C27 H26 N2 O'
_chemical_formula_weight         394.50
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-09-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-01-02 deposited with the CCDC.	2022-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                75.304(3)
_cell_angle_beta                 85.678(3)
_cell_angle_gamma                67.535(4)
_cell_formula_units_Z            2
_cell_length_a                   7.8864(3)
_cell_length_b                   9.9577(4)
_cell_length_c                   15.3148(4)
_cell_measurement_reflns_used    5113
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.0250
_cell_measurement_theta_min      4.9670
_cell_volume                     1074.74(7)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2169
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.967
_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   -106.00 -17.00   1.00    2.00    --  -40.80 -57.00 -90.00   89
  2  \w   -114.00 -39.00   1.00    2.00    --  -40.80 178.00  60.00   75
  3  \w    -66.00  32.00   1.00    2.00    --  -40.80  57.00  60.00   98
  4  \w     66.00  91.00   1.00    2.00    --   40.80 178.00 -60.00   25
  5  \w     74.00 103.00   1.00    4.00    --   99.68 -94.00 -30.00   29
  6  \w    112.00 165.00   1.00    4.00    --   99.68 125.00 -60.00   53
  7  \w     33.00  99.00   1.00    4.00    --   99.68 -77.00  30.00   66
  8  \w     83.00 113.00   1.00    4.00    --   99.68-125.00 150.00   30
  9  \w     29.00 127.00   1.00    4.00    --   99.68 -61.00-120.00   98
 10  \w     25.00  52.00   1.00    4.00    --   99.68 -94.00 -30.00   27
 11  \w     38.00  65.00   1.00    4.00    --   99.68-125.00 150.00   27
 12  \w    130.00 168.00   1.00    4.00    --   99.68  77.00-150.00   38
 13  \w     38.00  80.00   1.00    4.00    --   99.68-125.00-180.00   42
 14  \w     84.00 112.00   1.00    4.00    --   99.68-125.00-180.00   28
 15  \w     87.00 171.00   1.00    4.00    --   99.68  45.00  30.00   84
 16  \w     17.00 106.00   1.00    4.00    --   99.68 -94.00-120.00   89
 17  \w     51.00 174.00   1.00    4.00    --   99.68   0.00   0.00  123
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1411734000
_diffrn_orient_matrix_UB_12      0.0751547000
_diffrn_orient_matrix_UB_13      -0.0107522000
_diffrn_orient_matrix_UB_21      -0.1565229000
_diffrn_orient_matrix_UB_22      0.1521747000
_diffrn_orient_matrix_UB_23      -0.0020181000
_diffrn_orient_matrix_UB_31      0.0167521000
_diffrn_orient_matrix_UB_32      -0.0315867000
_diffrn_orient_matrix_UB_33      0.1034487000
_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  0.0171
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7116
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.053
_diffrn_reflns_theta_min         4.956
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.576
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79623
_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_density_diffrn    1.219
_exptl_crystal_description       block
_exptl_crystal_F_000             420
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.168
_refine_diff_density_min         -0.150
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.0120(9)
_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   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3956
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0407
_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^)+(0.0623P)^2^+0.1556P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1111
_refine_ls_wR_factor_ref         0.1142
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3634
_reflns_number_total             3956
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03504a2.cif
_cod_data_source_block           cxc-4-me
_cod_depositor_comments
'Adding full bibliography for 1567652--1567653.cif.'
_cod_database_code               1567653
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         C20H20N2
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C1(H1)
1.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C21(H21A,H21B)
1.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C12(H12), C20(H20), C6(H6), C8(H8), C16(H16), C11(H11), C23(H23),
 C27(H27), C9(H9), C5(H5), C10(H10), C17(H17), C26(H26), C25(H25), C24(H24),
 C19(H19), C18(H18)
1.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
;
_shelx_res_checksum              2894
_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 1.408
_oxdiff_exptl_absorpt_empirical_full_min 0.636