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_1558174
_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_formula_moiety         'C18 H18 N2 O2 S'
_chemical_formula_sum            'C18 H18 N2 O2 S'
_chemical_formula_weight         326.40
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-24
_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                90
_cell_angle_beta                 103.1000(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.60950(10)
_cell_length_b                   17.7870(2)
_cell_length_c                   14.05220(10)
_cell_measurement_reflns_used    24258
_cell_measurement_temperature    93.15
_cell_measurement_theta_max      76.1110
_cell_measurement_theta_min      4.0650
_cell_volume                     1609.03(3)
_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 0.997
_diffrn_measured_fraction_theta_max 0.970
_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   -119.00 -61.00   0.50    0.05    --  -47.82-152.00  13.00  116
  2  \w   -111.00 -33.00   0.50    0.05    --  -47.82 152.00  56.00  156
  3  \w    -94.00 -18.00   0.50    0.05    --  -47.82 122.00-104.00  152
  4  \w     13.00  94.00   0.50    0.05    --   47.82-122.00 173.00  162
  5  \w     55.00 120.00   0.50    0.05    --   47.82 152.00  56.00  130
  6  \w     27.00 112.00   0.50    0.05    --   47.82-152.00  13.00  170
  7  \w   -169.00 -61.00   0.50    0.05    -- -100.00-152.00  13.00  216
  8  \w   -173.00 -81.00   0.50    0.05    -- -100.00-122.00 173.00  184
  9  \w   -135.00 -33.00   0.50    0.05    -- -100.00 152.00  56.00  204
 10  \w   -114.00 -27.00   0.50    0.05    -- -100.00 122.00-104.00  174
 11  \w     34.00 135.00   0.50    0.05    --  106.49-152.00  13.00  202
 12  \w     34.00 114.00   0.50    0.05    --  106.49-122.00 173.00  160
 13  \w     75.00 174.00   0.50    0.05    --  106.49 122.00-104.00  198
 14  \w     55.00 169.00   0.50    0.05    --  106.49 152.00  56.00  228
 15  \w     25.00 120.00   0.50    0.05    --   47.82  77.00 -30.00  190
 16  \w    -25.00  60.00   0.50    0.05    --   47.82 -38.00 -60.00  170
 17  \w     73.00 120.00   0.50    0.05    --   47.82 125.00-150.00   94
 18  \w    -23.00  63.00   0.50    0.05    --   47.82 -57.00-150.00  172
 19  \w    -67.00 -25.00   0.50    0.05    -- -100.00  30.00 -60.00   84
 20  \w   -116.00 -27.00   0.50    0.05    -- -100.00  61.00  90.00  178
 21  \w    -67.00 -25.00   0.50    0.05    -- -100.00  30.00 -30.00   84
 22  \w   -123.00 -27.00   0.50    0.05    -- -100.00  77.00  90.00  192
 23  \w   -117.00 -27.00   0.50    0.05    -- -100.00 125.00  60.00  180
 24  \w    -81.00 -28.00   0.50    0.05    -- -100.00  45.00 -60.00  106
 25  \w    -67.00 -25.00   0.50    0.05    -- -100.00  30.00-120.00   84
 26  \w    -67.00 -25.00   0.50    0.05    -- -100.00  30.00 -90.00   84
 27  \w    -67.00 -25.00   0.50    0.05    -- -100.00  30.00-150.00   84
 28  \w     31.00 120.00   0.50    0.05    --  106.49 -15.00 150.00  178
 29  \w     34.00 108.00   0.50    0.05    --  106.49 -94.00-180.00  148
 30  \w     35.00  75.00   0.50    0.05    --  106.49 -45.00 -30.00   80
 31  \w     34.00 108.00   0.50    0.05    --  106.49 -94.00 120.00  148
 32  \w     33.00  59.00   0.50    0.05    --  106.49 -30.00 120.00   52
 33  \w     32.00  61.00   0.50    0.05    --  106.49 -30.00 -30.00   58
 34  \w     35.00  60.00   0.50    0.05    --  106.49 -30.00 -60.00   50
 35  \w     50.00 108.00   0.50    0.05    --  106.49 -94.00-150.00  116
 36  \w     42.00  72.00   0.50    0.05    --  106.49 -45.00   0.00   60
 37  \w     35.00  75.00   0.50    0.05    --  106.49 -45.00  30.00   80
 38  \w     32.00  61.00   0.50    0.05    --  106.49 -30.00 -90.00   58
 39  \w     36.00  68.00   0.50    0.05    --  106.49 -45.00 120.00   64
 40  \w     37.00  63.00   0.50    0.05    --  106.49 -45.00 -60.00   52
;
_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      -0.0281357000
_diffrn_orient_matrix_UB_12      -0.0708592000
_diffrn_orient_matrix_UB_13      -0.0647938000
_diffrn_orient_matrix_UB_21      0.0800250000
_diffrn_orient_matrix_UB_22      -0.0490128000
_diffrn_orient_matrix_UB_23      0.0910970000
_diffrn_orient_matrix_UB_31      -0.2237202000
_diffrn_orient_matrix_UB_32      -0.0086046000
_diffrn_orient_matrix_UB_33      0.0135038000
_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  0.0363
_diffrn_reflns_av_unetI/netI     0.0164
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            30088
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.354
_diffrn_reflns_theta_min         4.076
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    1.878
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75225
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.347
_exptl_crystal_description       needle
_exptl_crystal_F_000             688
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.452
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         3278
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0667
_refine_ls_R_factor_gt           0.0653
_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^)+(0.0878P)^2^+1.6709P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1730
_refine_ls_wR_factor_ref         0.1739
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3168
_reflns_number_total             3278
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc01890b2.cif
_cod_data_source_block           exp_241
_cod_depositor_comments
'Adding full bibliography for 1558174--1558176.cif.'
_cod_database_code               1558174
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_chemical_oxdiff_usercomment     santosh
_reflns_odcompleteness_completeness 99.70
_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:
 C00L(H00J,H00L), C00N(H00P,H00Q)
2.b Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00A), C00B(H00B), C00D(H00D), C00E(H00E), C00G(H00G),
 C00H(H00H), C00K(H00K)
2.c Idealised Me refined as rotating group:
 C00I(H00C,H00F,H00I), C00M(H00M,H00N,H00O)
;
_shelx_res_checksum              6289
_shelx_hkl_checksum              74069
_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 1.576
_oxdiff_exptl_absorpt_empirical_full_min 0.558