Introduction of a 7-aza-6-MeO-indoline auxiliary in Lewis-acid/photoredox cooperative catalysis: highly enantioselective aminomethylation of α,β-unsaturated amides
Pagire, Santosh K.; Kumagai, Naoya; Shibasaki, Masakatsu; Chemical Science 11 (2020) 5168–5174; doi:10.1039/D0SC01890B

data_1558175
_publ_section_title
;
 Introduction of a 7-aza-6-MeO-indoline auxiliary in Lewis-acid/photoredox
 cooperative catalysis: highly enantioselective aminomethylation of
 \a,\b-unsaturated amides
;
_journal_issue                   20
_journal_name_full               'Chemical Science'
_journal_page_first              5168
_journal_page_last               5174
_journal_paper_doi               10.1039/D0SC01890B
_journal_volume                  11
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C19 H23 N3 O2'
_chemical_formula_sum            'C19 H23 N3 O2'
_chemical_formula_weight         325.40
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-02-19 deposited with the CCDC.	2020-04-27 downloaded from the CCDC.
;
_cell_angle_alpha                103.6280(10)
_cell_angle_beta                 98.2720(10)
_cell_angle_gamma                101.1120(10)
_cell_formula_units_Z            2
_cell_length_a                   6.05710(10)
_cell_length_b                   10.16470(10)
_cell_length_c                   14.3715(2)
_cell_measurement_reflns_used    19825
_cell_measurement_temperature    93.15
_cell_measurement_theta_max      76.2910
_cell_measurement_theta_min      3.2040
_cell_volume                     827.01(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_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_temperature      93.15
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.965
_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     25.00 120.00   0.50    0.05    --   47.95  77.00 -30.00  190
  2  \w     69.00 120.00   0.50    0.05    --   47.95 132.00-137.00  102
  3  \w     69.00 174.00   0.50    0.12    --  106.49 132.00-137.00  210
  4  \w     91.00 116.00   0.50    0.12    --  106.49  61.00 -60.00   50
  5  \w     65.00 174.00   0.50    0.12    --  106.49 138.00  38.00  218
  6  \w     90.00 136.00   0.50    0.12    --  106.49  61.00  60.00   92
  7  \w     65.00 120.00   0.50    0.05    --   47.95 138.00  38.00  110
  8  \w     25.00 120.00   0.50    0.05    --   47.95  77.00 120.00  190
  9  \w     33.00 119.00   0.50    0.05    --   47.95  57.00 -60.00  172
 10  \w     36.00 121.00   0.50    0.05    --   47.95  38.00  30.00  170
 11  \w    104.00 129.00   0.50    0.12    --  106.49 -77.00 120.00   50
 12  \w     76.00 102.00   0.50    0.12    --  106.49 -77.00 120.00   52
 13  \w     36.00  75.00   0.50    0.12    --  106.49 -45.00   0.00   78
 14  \w     34.00  93.00   0.50    0.12    --  106.49 -94.00 -30.00  118
 15  \w     64.00 108.00   0.50    0.12    --  106.49 -94.00   0.00   88
 16  \w     38.00 121.00   0.50    0.12    --  106.49 -61.00 120.00  166
 17  \w     41.00 117.00   0.50    0.12    --  106.49-132.00 152.00  152
 18  \w     37.00  63.00   0.50    0.12    --  106.49 -94.00   0.00   52
 19  \w     34.00 126.00   0.50    0.12    --  106.49-138.00 -23.00  184
 20  \w     21.00 103.00   0.50    0.05    --   47.95-138.00 -23.00  164
 21  \w     18.00  99.00   0.50    0.05    --   47.95-132.00 152.00  162
 22  \w     36.00 121.00   0.50    0.05    --   47.95  38.00  90.00  170
 23  \w     36.00 121.00   0.50    0.05    --   47.95  38.00 -90.00  170
 24  \w     36.00 121.00   0.50    0.05    --   47.95  38.00-150.00  170
 25  \w     25.00 120.00   0.50    0.05    --   47.95  77.00-120.00  190
 26  \w     25.00 120.00   0.50    0.05    --   47.95  77.00-180.00  190
 27  \w     25.00 120.00   0.50    0.05    --   47.95  77.00   0.00  190
 28  \w     25.00 120.00   0.50    0.05    --   47.95  77.00 150.00  190
 29  \w     33.00 119.00   0.50    0.05    --   47.95  57.00  90.00  172
 30  \w     25.00 120.00   0.50    0.05    --   47.95  77.00  60.00  190
 31  \w    -80.00 -28.00   0.50    0.12    -- -100.00  45.00 -90.00  104
 32  \w   -103.00 -27.00   0.50    0.05    --  -47.95 138.00  38.00  152
 33  \w    -99.00 -24.00   0.50    0.05    --  -47.95 132.00-137.00  150
 34  \w   -121.00 -27.00   0.50    0.12    -- -100.00 132.00-137.00  188
 35  \w   -126.00 -27.00   0.50    0.12    -- -100.00 138.00  38.00  198
 36  \w   -119.00 -33.00   0.50    0.05    --  -47.95 -57.00 -30.00  172
 37  \w   -103.00 -78.00   0.50    0.12    -- -100.00 -74.00 -66.84   50
 38  \w   -108.00 -83.00   0.50    0.12    -- -100.00 -61.00-120.00   50
 39  \w   -110.00 -77.00   0.50    0.12    -- -100.00 -77.00-120.00   66
 40  \w   -108.00 -78.00   0.50    0.12    -- -100.00 -74.00 -91.86   60
 41  \w   -103.00 -77.00   0.50    0.12    -- -100.00 -77.00 -30.00   52
 42  \w   -103.00 -77.00   0.50    0.12    -- -100.00 -77.00  30.00   52
 43  \w   -104.00 -77.00   0.50    0.12    -- -100.00 -77.00  90.00   54
 44  \w   -103.00 -77.00   0.50    0.12    -- -100.00 -77.00  60.00   52
 45  \w   -105.00 -78.00   0.50    0.12    -- -100.00 -84.00 145.15   54
 46  \w   -100.00 -75.00   0.50    0.12    -- -100.00 -82.00 167.57   50
 47  \w   -117.00 -90.00   0.50    0.12    -- -100.00 -58.00 155.13   54
 48  \w   -130.00 -82.00   0.50    0.12    -- -100.00 -64.00 107.20   96
 49  \w   -120.00 -70.00   0.50    0.05    --  -47.95-138.00 -23.00  100
 50  \w   -120.00 -25.00   0.50    0.05    --  -47.95 -77.00 -90.00  190
 51  \w   -104.00 -77.00   0.50    0.12    -- -100.00 -78.00 -37.63   54
 52  \w   -119.00 -87.00   0.50    0.12    -- -100.00 -53.00 -77.13   64
 53  \w   -123.00 -87.00   0.50    0.12    -- -100.00 -61.00 -90.00   72
 54  \w   -118.00 -84.00   0.50    0.12    -- -100.00 -61.00-176.33   68
 55  \w   -120.00 -25.00   0.50    0.05    --  -47.95 -77.00-150.00  190
 56  \w   -172.00 -86.00   0.50    0.12    -- -100.00 -44.00  54.44  172
 57  \w   -155.00 -83.00   0.50    0.12    -- -100.00 -61.00 174.43  144
 58  \w   -173.00 -75.00   0.50    0.12    -- -100.00-132.00 152.00  196
 59  \w   -170.00 -83.00   0.50    0.12    -- -100.00 -61.00  90.00  174
 60  \w   -173.00 -70.00   0.50    0.12    -- -100.00-138.00 -23.00  206
 61  \w   -164.00-126.00   0.50    0.12    -- -100.00 -61.00-120.00   76
 62  \w   -173.00 -74.00   0.50    0.12    -- -100.00 -83.00-130.36  198
 63  \w   -173.00 -83.00   0.50    0.12    -- -100.00 -61.00  60.00  180
 64  \w   -173.00 -74.00   0.50    0.12    -- -100.00 -83.00   3.08  198
 65  \w   -173.00 -77.00   0.50    0.12    -- -100.00 -77.00-150.00  192
 66  \w   -172.00-123.00   0.50    0.12    -- -100.00 -74.00 -66.84   98
 67  \w   -173.00 -76.00   0.50    0.12    -- -100.00 -79.00  17.51  194
 68  \w   -171.00 -85.00   0.50    0.12    -- -100.00 -58.00-131.38  172
 69  \w   -173.00 -81.00   0.50    0.12    -- -100.00 -68.00 -27.36  184
 70  \w   -173.00 -77.00   0.50    0.12    -- -100.00 -77.00 150.00  192
 71  \w   -172.00 -85.00   0.50    0.12    -- -100.00 -55.00 157.36  174
 72  \w   -173.00 -83.00   0.50    0.12    -- -100.00 -61.00  30.00  180
 73  \w   -173.00 -83.00   0.50    0.12    -- -100.00 -62.00  87.99  180
 74  \w   -172.00-107.00   0.50    0.12    -- -100.00 -82.00 167.57  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-Custom'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0504164000
_diffrn_orient_matrix_UB_12      0.0240889000
_diffrn_orient_matrix_UB_13      0.1116597000
_diffrn_orient_matrix_UB_21      0.0700791000
_diffrn_orient_matrix_UB_22      0.1583805000
_diffrn_orient_matrix_UB_23      0.0137790000
_diffrn_orient_matrix_UB_31      -0.2499737000
_diffrn_orient_matrix_UB_32      0.0092548000
_diffrn_orient_matrix_UB_33      0.0027499000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0482
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            29128
_diffrn_reflns_point_group_measured_fraction_full 0.939
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.326
_diffrn_reflns_theta_min         3.228
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    0.689
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51568
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14a (Rigaku Oxford Diffraction, 2018)
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    1.307
_exptl_crystal_description       plate
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.008
_refine_diff_density_max         0.227
_refine_diff_density_min         -0.278
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 2647 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     437
_refine_ls_number_reflns         6188
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0368
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0621P)^2^+0.0808P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0957
_refine_ls_wR_factor_ref         0.0966
_reflns_Friedel_coverage         0.846
_reflns_Friedel_fraction_full    0.879
_reflns_Friedel_fraction_max     0.817
_reflns_number_gt                5982
_reflns_number_total             6188
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc01890b2.cif
_cod_data_source_block           exp_261
_cod_depositor_comments
;
Adding full bibliography for 1558174--1558176.cif.

2022-05-28
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C19 H23 N3 O2)'
_cod_original_formula_sum        'C38 H46 N6 O4'
_cod_original_formula_units_Z    1
_cod_original_formula_weight     650.81
_cod_database_code               1558175
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     'GABA-Final-Aniline der'
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.820
_reflns_odcompleteness_completeness 100.00
_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.a Ternary CH refined with riding coordinates:
 C012(H012), C019(H019)
2.b Secondary CH2 refined with riding coordinates:
 C00Y(H00B,H00C), C010(H01M,H01N), C011(H01O,H01P), C013(H01Q,H01R), C015(H01A,
 H01B), C016(H01C,H01D), C017(H01V,H01W), C018(H01E,H01F)
2.c Aromatic/amide H refined with riding coordinates:
 N009(H009), N00A(H00A), C00H(H00H), C00J(H00J), C00L(H00L), C00M(H00M),
 C00N(H00N), C00O(H00O), C00P(H00P), C00Q(H00Q), C00S(H00S), C00U(H00U),
 C00V(H00V), C00W(H00W), C00X(H00X), C00Z(H00Z)
2.d Idealised Me refined as rotating group:
 C014(H01S,H01T,H01U), C01A(H01G,H01H,H01I), C01B(H01X,H01Y,H), C01C(H01J,H01K,
 H01L)
;
_shelx_res_checksum              15387
_shelx_hkl_checksum              63921
_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 1.434
_oxdiff_exptl_absorpt_empirical_full_min 0.573