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_1558176
_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         'C68 H63 Cu N3 O2 P2, F6 P, 3(C4 H8 O)'
_chemical_formula_sum            'C80 H87 Cu F6 N3 O5 P3'
_chemical_formula_weight         1440.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-23
_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                 106.505(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.7889(4)
_cell_length_b                   16.4491(4)
_cell_length_c                   24.0629(5)
_cell_measurement_reflns_used    25104
_cell_measurement_temperature    93.15
_cell_measurement_theta_max      76.6650
_cell_measurement_theta_min      2.0980
_cell_volume                     8269.0(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 0.999
_diffrn_measured_fraction_theta_max 0.971
_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  59.00   0.50   11.85    --   47.95 -38.00  30.00  168
  2  \w     16.00  90.00   0.50   11.85    --   47.95-119.00 -86.00  148
  3  \w     55.00 110.00   0.50   48.39    --  106.49-119.00 -86.00  110
  4  \w     62.00 117.00   0.50   48.39    --  106.49-125.00-120.00  110
  5  \w     46.00  96.00   0.50   48.39    --  106.49 -94.00 -60.00  100
  6  \w     77.00 116.00   0.50   48.39    --  106.49 -15.00-150.00   78
  7  \w     35.00  65.00   0.50   48.39    --  106.49 -45.00 -90.00   60
  8  \w     36.00  75.00   0.50   48.39    --  106.49 -45.00 -30.00   78
  9  \w     32.00  57.00   0.50   48.39    --  106.49 -30.00  30.00   50
 10  \w     43.00 122.00   0.50   48.39    --  106.49 -61.00  60.00  158
 11  \w     72.00 102.00   0.50   11.85    --   47.95-157.00 118.00   60
 12  \w     35.00 138.00   0.50   48.39    --  106.49-157.00 118.00  206
 13  \w     34.00  90.00   0.50   48.39    --  106.49 -77.00  60.00  112
 14  \w     35.00  75.00   0.50   48.39    --  106.49 -45.00 150.00   80
 15  \w     41.00  74.00   0.50   48.39    --  106.49 -45.00 120.00   66
 16  \w     34.00  60.00   0.50   48.39    --  106.49 -30.00  90.00   52
 17  \w     77.00 141.00   0.50   48.39    --  106.49 119.00  -1.00  128
 18  \w     75.00 119.00   0.50   11.85    --   47.95 125.00 -60.00   88
 19  \w     77.00 120.00   0.50   11.85    --   47.95 125.00 -30.00   86
 20  \w     57.00 115.00   0.50   11.85    --   47.95 157.00 154.00  116
 21  \w     64.00  90.00   0.50   48.39    --  106.49 157.00 154.00   52
 22  \w     40.00  74.00   0.50   48.39    --  106.49 -45.00-120.00   68
 23  \w     31.00  74.00   0.50   48.39    --  106.49 -15.00-150.00   86
 24  \w     32.00  57.00   0.50   48.39    --  106.49 -30.00-150.00   50
 25  \w      0.00  58.00   0.50   11.85    --   47.95 -38.00-150.00  116
 26  \w    -99.00 -74.00   0.50   11.85    --  -47.95 157.00 154.00   50
 27  \w    -90.00 -28.00   0.50   11.85    --  -47.95 119.00  -1.00  124
 28  \w    -76.00 -27.00   0.50   48.39    -- -100.00  61.00  30.00   98
 29  \w    -57.00 -25.00   0.50   48.39    -- -100.00  30.00  60.00   64
 30  \w    -55.00 -26.00   0.50   48.39    -- -100.00  30.00  30.00   58
 31  \w    -52.00 -27.00   0.50   48.39    -- -100.00 125.00 120.00   50
 32  \w    -67.00 -26.00   0.50   48.39    -- -100.00  30.00 150.00   82
 33  \w   -112.00 -65.00   0.50   48.39    -- -100.00 119.00  -1.00   94
 34  \w   -115.00 -89.00   0.50   48.39    -- -100.00  61.00  30.00   52
 35  \w   -117.00 -72.00   0.50   48.39    -- -100.00 125.00 120.00   90
 36  \w   -101.00 -38.00   0.50   48.39    -- -100.00 157.00 154.00  126
 37  \w   -115.00 -83.00   0.50   48.39    -- -100.00 125.00  60.00   64
 38  \w    -54.00 -25.00   0.50   48.39    -- -100.00  30.00-120.00   58
 39  \w    -59.00 -34.00   0.50   48.39    -- -100.00  30.00-150.00   50
 40  \w    -80.00 -33.00   0.50   48.39    -- -100.00  45.00-180.00   94
 41  \w   -152.00-127.00   0.50   48.39    -- -100.00-119.00 -86.00   50
 42  \w   -170.00-117.00   0.50   48.39    -- -100.00-125.00-150.00  106
 43  \w   -113.00 -88.00   0.50   11.85    --  -47.95-157.00 118.00   50
 44  \w   -136.00-111.00   0.50   48.39    -- -100.00-157.00 118.00   50
 45  \w   -136.00 -80.00   0.50   48.39    -- -100.00-125.00 150.00  112
 46  \w   -120.00 -28.00   0.50   11.85    --  -47.95 -77.00 120.00  184
;
_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      0.0086480000
_diffrn_orient_matrix_UB_12      0.0672668000
_diffrn_orient_matrix_UB_13      0.0462526000
_diffrn_orient_matrix_UB_21      -0.0043255000
_diffrn_orient_matrix_UB_22      -0.0641046000
_diffrn_orient_matrix_UB_23      0.0453421000
_diffrn_orient_matrix_UB_31      0.0730739000
_diffrn_orient_matrix_UB_32      -0.0117099000
_diffrn_orient_matrix_UB_33      0.0163633000
_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  0.1098
_diffrn_reflns_av_unetI/netI     0.0668
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            118804
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.010
_diffrn_reflns_theta_min         2.115
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    1.422
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78817
_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    1.157
_exptl_crystal_description       plate
_exptl_crystal_F_000             3024
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.008
_refine_diff_density_max         0.470
_refine_diff_density_min         -0.671
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     892
_refine_ls_number_reflns         17003
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1027
_refine_ls_R_factor_gt           0.0680
_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^)+(0.1181P)^2^+1.4880P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1866
_refine_ls_wR_factor_ref         0.2118
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10842
_reflns_number_total             17003
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc01890b2.cif
_cod_data_source_block           exp_262
_cod_depositor_comments
'Adding full bibliography for 1558174--1558176.cif.'
_cod_database_code               1558176
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H Cu P F N O'
_chemical_oxdiff_usercomment     'Cu-Phosphine Pyrdine complex'
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.764
_reflns_odcompleteness_completeness 99.95
_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:
 C01M(H01J,H01L), C026(H02A,H02B), C02C(H02Z,HA), C02E(H02R,H02S), C02F(H02T,
 H02U), C02G(H02V,H02W), C02H(H02,HB), C02J(H0AA,HC), C02L(H1AA,HD), C02O(H2AA,
 HE), C02P(H02X,H02Y), C02Q(H3AA,HF), C02R(H4AA,HG), C02S(H5AA,HH)
2.b Aromatic/amide H refined with riding coordinates:
 C36(H36), C00K(H00K), C00O(H00O), C00P(H00P), C00Q(H00Q), C00T(H00T),
 C00V(H00V), C00Y(H00Y), C00Z(H00Z), C010(H010), C012(H012), C013(H013),
 C015(H015), C017(H017), C019(H019), C01A(H01D), C01C(H01E), C01E(H01F),
 C01G(H01G), C01H(H01H), C01I(H01I), C01K(H01K), C01N(H01N), C01O(H01O),
 C01S(H01S), C01U(H01U), C01X(H01X), C020(H020), C021(H021), C023(H023),
 C025(H025), C027(H027)
2.c Idealised Me refined as rotating group:
 C018(H01A,H01B,H01C), C01T(H01M,H01P,H01Q), C01Y(H01R,H01T,H01V), C01Z(H01W,
 H01Y,H), C028(H02C,H02D,H02E), C029(H02F,H02G,H02H), C02B(H02I,H02J,H02K),
 C02D(H02L,H02M,H02N), C02I(H02O,H02P,H02Q)
;
_shelx_res_checksum              10673
_shelx_hkl_checksum              90724
_shelx_fab_checksum              62627
_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 1.958
_oxdiff_exptl_absorpt_empirical_full_min 0.658