Metal-free, visible-light induced enantioselective three-component dicarbofunctionalization and oxytrifluoromethylation of enamines via chiral phosphoric acid catalysis
Liang, Hui; Ji, Dong-Sheng; Xu, Guo-Qiang; Luo, Yong-Chun; Zheng, Haixue; Xu, Peng-Fei; Chemical Science 13 (2022) 1088–1094; doi:10.1039/D1SC06613G

data_1565908
_publ_section_title
;
 Metal-free, visible-light induced enantioselective three-component
 dicarbofunctionalization and oxytrifluoromethylation of enamines via
 chiral phosphoric acid catalysis
;
_journal_issue                   4
_journal_name_full               'Chemical Science'
_journal_page_first              1088
_journal_page_last               1094
_journal_paper_doi               10.1039/D1SC06613G
_journal_volume                  13
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H26 N2 O3'
_chemical_formula_sum            'C23 H26 N2 O3'
_chemical_formula_weight         378.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-06
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2021-09-07 deposited with the CCDC.	2021-12-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.7120(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.42390(10)
_cell_length_b                   10.06990(10)
_cell_length_c                   11.23500(10)
_cell_measurement_reflns_used    9557
_cell_measurement_temperature    298.30(10)
_cell_measurement_theta_max      77.3440
_cell_measurement_theta_min      4.8360
_cell_volume                     1035.789(18)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298.30(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.958
_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     93.00 174.00   0.50    0.05    --  107.75  77.00-120.00  162
  2  \w     98.00 170.00   0.50    0.05    --  107.75  37.00-180.00  144
  3  \w    111.00 171.00   0.50    0.05    --  107.75  37.00-150.00  120
  4  \w    124.00 150.00   0.50    0.05    --  107.75  37.00-120.00   52
  5  \w     97.00 123.00   0.50    0.05    --  107.75  37.00-120.00   52
  6  \w    139.00 172.00   0.50    0.05    --  107.75  37.00  60.00   66
  7  \w    100.00 135.00   0.50    0.05    --  107.75  37.00  60.00   70
  8  \w    142.00 175.00   0.50    0.05    --  107.75  83.00 -85.00   66
  9  \w     38.00  63.00   0.50    0.05    --  107.75 -57.00-150.00   50
 10  \w    -27.00   8.00   0.50    0.05    --   47.57 -19.00-180.00   70
 11  \w    -26.00  19.00   0.50    0.05    --   47.57 -19.00-120.00   90
 12  \w     35.00  60.00   0.50    0.05    --  107.75 -57.00 -60.00   50
 13  \w     35.00  60.00   0.50    0.05    --  107.75 -57.00   0.00   50
 14  \w     38.00  63.00   0.50    0.05    --  107.75 -57.00  30.00   50
 15  \w     63.00  94.00   0.50    0.05    --   47.57-125.00  60.00   62
 16  \w     31.00  56.00   0.50    0.05    --   47.57-125.00  60.00   50
 17  \w     -5.00  41.00   0.50    0.05    --   47.57 -83.00 153.00   92
 18  \w     60.00  85.00   0.50    0.05    --  107.75 -83.00 153.00   50
 19  \w     80.00 106.00   0.50    0.05    --  107.75 -99.00 120.00   52
 20  \w     64.00  99.00   0.50    0.05    --  107.75 -99.00 -90.00   70
 21  \w     58.00  99.00   0.50    0.05    --  107.75 -99.00-120.00   82
 22  \w    -62.00 -18.00   0.50    0.05    --  -47.57  83.00 -85.00   88
 23  \w    -15.00  12.00   0.50    0.05    --  -47.57  83.00 -85.00   54
 24  \w   -106.00 -80.00   0.50    0.05    -- -100.00  83.00 -85.00   52
 25  \w   -106.00 -27.00   0.50    0.05    -- -100.00 125.00 150.00  158
 26  \w    -58.00 -30.00   0.50    0.05    -- -100.00  57.00 120.00   56
 27  \w    -58.00 -28.00   0.50    0.05    -- -100.00  57.00  90.00   60
 28  \w    -61.00 -28.00   0.50    0.05    --  -47.57  57.00 120.00   66
 29  \w    -18.00  21.00   0.50    0.05    --  -47.57  57.00 120.00   78
 30  \w   -109.00 -83.00   0.50    0.05    -- -100.00  77.00-150.00   52
 31  \w    -68.00 -42.00   0.50    0.05    -- -100.00  57.00-150.00   52
 32  \w    -53.00 -28.00   0.50    0.05    -- -100.00  77.00-150.00   50
 33  \w   -175.00-129.00   0.50    0.05    -- -100.00 -19.00  60.00   92
 34  \w   -122.00 -85.00   0.50    0.05    -- -100.00 -77.00  90.00   74
 35  \w   -111.00 -25.00   0.50    0.05    --  -47.57 -77.00 120.00  172
 36  \w   -121.00 -81.00   0.50    0.05    -- -100.00 -77.00 120.00   80
 37  \w   -170.00-137.00   0.50    0.05    -- -100.00 -77.00  90.00   66
 38  \w   -169.00-127.00   0.50    0.05    -- -100.00 -37.00  30.00   84
 39  \w   -123.00 -87.00   0.50    0.05    -- -100.00 -37.00  30.00   72
 40  \w   -169.00-136.00   0.50    0.05    -- -100.00 -77.00 120.00   66
 41  \w   -173.00 -84.00   0.50    0.05    -- -100.00 -83.00 153.00  178
;
_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      0.0456165000
_diffrn_orient_matrix_UB_12      -0.1093028000
_diffrn_orient_matrix_UB_13      -0.0793717000
_diffrn_orient_matrix_UB_21      0.0717387000
_diffrn_orient_matrix_UB_22      -0.0782647000
_diffrn_orient_matrix_UB_23      0.1165520000
_diffrn_orient_matrix_UB_31      -0.1452222000
_diffrn_orient_matrix_UB_32      -0.0730220000
_diffrn_orient_matrix_UB_33      -0.0061477000
_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  0.0209
_diffrn_reflns_av_unetI/netI     0.0204
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            11587
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.509
_diffrn_reflns_theta_min         4.830
_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  0.70860
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.213
_exptl_crystal_description       block
_exptl_crystal_F_000             404
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.157
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 1770 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     270
_refine_ls_number_reflns         4103
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.113
_refine_ls_R_factor_all          0.0342
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0526P)^2^+0.0654P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0878
_refine_ls_wR_factor_ref         0.0884
_reflns_Friedel_coverage         0.837
_reflns_Friedel_fraction_full    0.987
_reflns_Friedel_fraction_max     0.902
_reflns_number_gt                3994
_reflns_number_total             4103
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06613g2.cif
_cod_data_source_block           lianghui_0706_auto
_cod_depositor_comments          'Adding full bibliography for 1565908.cif.'
_cod_database_code               1565908
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 98.22
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C20-C23 \\sim C20-C24
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.005
4. Others
 Fixed Sof: C23(0.6) H23A(0.6) H23B(0.6) H23C(0.6) C24(0.4) H24A(0.4)
 H24B(0.4) H24C(0.4)
5.a Ternary CH refined with riding coordinates:
 C9(H9)
5.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B)
5.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C5(H5), C8(H8), C14(H14), C2(H2A), C3(H3), C4(H4), C18(H18), C15(H15),
  C16(H16), C17(H17)
5.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C)
;
_shelx_res_checksum              86201
_shelx_hkl_checksum              15142
_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 1.312
_oxdiff_exptl_absorpt_empirical_full_min 0.834