Electrochemical dual α,β-C(sp3)–H functionalization of cyclic N-aryl amines
Feng, Tian; Zhu, Zile; Zhang, Dongmei; Wang, Siyi; Li, Ruopu; Zhu, Zhaolin; Zhang, Xinxing; Qiu, Youai; Green Chemistry 25 (2023) 2681–2689; doi:10.1039/D3GC00344B

data_7246418
_publ_section_title
;
 Electrochemical dual \a,\b-C(sp3)--H functionalization of cyclic N-aryl
 amines
;
_journal_issue                   7
_journal_name_full               'Green Chemistry'
_journal_page_first              2681
_journal_page_last               2689
_journal_paper_doi               10.1039/D3GC00344B
_journal_volume                  25
_journal_year                    2023
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C20 H19 N O2'
_chemical_formula_sum            'C20 H19 N O2'
_chemical_formula_weight         305.36
_chemical_name_systematic
(4R,7aR)-4-methyl-3,7-diphenyl-5,6,7,7a-tetrahydrofuro[2,3-b]pyridin-2(4H)-one
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2022-11-10 deposited with the CCDC.	2023-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.58017(5)
_cell_length_b                   9.58017(5)
_cell_length_c                   33.7964(3)
_cell_measurement_reflns_used    9981
_cell_measurement_temperature    100.01(16)
_cell_measurement_theta_max      75.7550
_cell_measurement_theta_min      4.7710
_cell_volume                     3101.82(4)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(16)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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    -53.00 -28.00   0.50    0.60    --    0.00 -25.00 -15.00   50
  2  \w    106.00 131.00   0.50    2.00    --  101.30  25.00 148.00   50
  3  \w     26.00  75.00   0.50    2.00    --  101.30 -25.00 -15.00   98
  4  \w    -36.00  39.00   0.50    0.60    --    0.00  82.00-150.00  150
  5  \w     76.00 191.00   0.50    2.00    --  101.30  38.00 -60.00  230
  6  \w     86.00 191.00   0.50    2.00    --  101.30  82.00  60.00  210
  7  \w     58.00  85.00   0.50    0.60    --    0.00  24.00 148.00   54
  8  \w    151.00 185.00   0.50    1.50    --  101.30  19.00 120.00   68
  9  \w     13.00  40.00   0.50    1.50    --  101.30 -38.00 -30.00   54
 10  \w     64.00 127.00   0.50    1.50    --  101.30 -38.00 -30.00  126
 11  \w     76.00 127.00   0.50    1.50    --  101.30  38.00 -30.00  102
 12  \w    144.00 170.00   0.50    1.50    --  101.30  38.00 -30.00   52
 13  \w     74.00 148.00   0.50    1.50    --  101.30  19.00 120.00  148
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0049067000
_diffrn_orient_matrix_UB_12      0.0204369000
_diffrn_orient_matrix_UB_13      0.0451985000
_diffrn_orient_matrix_UB_21      -0.1532732000
_diffrn_orient_matrix_UB_22      0.0473320000
_diffrn_orient_matrix_UB_23      -0.0030589000
_diffrn_orient_matrix_UB_31      -0.0482810000
_diffrn_orient_matrix_UB_32      -0.1523290000
_diffrn_orient_matrix_UB_33      0.0051230000
_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  0.0327
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            16868
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.945
_diffrn_reflns_theta_min         4.616
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    0.668
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78178
_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    1.308
_exptl_crystal_description       block
_exptl_crystal_F_000             1296
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Dichloromethane, Hexane'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.204
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 2683 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.28(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.142
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     417
_refine_ls_number_reflns         6166
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0518
_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^)+(0.0074P)^2^+4.1257P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1242
_refine_ls_wR_factor_ref         0.1247
_reflns_Friedel_coverage         0.908
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.926
_reflns_number_gt                6022
_reflns_number_total             6166
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc00344b2.cif
_cod_data_source_block           5-109
_cod_depositor_comments          'Adding full bibliography for 7246418.cif.'
_cod_database_code               7246418
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.82
_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 Ternary CH refined with riding coordinates:
 C7(H7), C10(H10), C29(H29), C32(H32)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C27(H27A,H27B), C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C36(H36),
  C37(H37), C38(H38), C39(H39), C40(H40)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              24040
_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 1.466
_oxdiff_exptl_absorpt_empirical_full_min 0.706