A Sc(OTf)3 catalyzed Mukaiyama–Mannich reaction of difluoroenoxysilanes with unactivated ketimines
Hu, Xiao-Si; Ding, Pei-Gang; Yu, Jin-Sheng; Zhou, Jian; Organic Chemistry Frontiers 6 (2019) 2500–; doi:10.1039/C9QO00577C

data_1554949
_publ_section_title
;
 A Sc(OTf)3 catalyzed Mukaiyama--Mannich reaction of difluoroenoxysilanes
 with unactivated ketimines
;
_journal_issue                   14
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              2500
_journal_paper_doi               10.1039/C9QO00577C
_journal_volume                  6
_journal_year                    2019
_chemical_formula_moiety         'C25 H23 F2 N O3 S'
_chemical_formula_sum            'C25 H23 F2 N O3 S'
_chemical_formula_weight         455.50
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_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             2018-12-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-12-12 deposited with the CCDC.	2019-05-30 downloaded from the CCDC.
;
_cell_angle_alpha                99.329(2)
_cell_angle_beta                 99.436(2)
_cell_angle_gamma                101.204(2)
_cell_formula_units_Z            2
_cell_length_a                   8.0332(2)
_cell_length_b                   8.5272(2)
_cell_length_c                   16.9075(4)
_cell_measurement_reflns_used    12928
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.1710
_cell_measurement_theta_min      5.3730
_cell_volume                     1097.99(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.976
_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     16.00  89.00   1.00    1.00    --    0.00  77.00  30.00   73
  2  \w    -19.00   7.00   1.00    1.00    --    0.00  38.00 -90.00   26
  3  \w    -12.00  21.00   1.00    1.00    --    0.00  38.00 120.00   33
  4  \w    -26.00  10.00   1.00    1.00    --    0.00  77.00  30.00   36
  5  \w     49.00  78.00   1.00    1.00    --    0.00  57.00 120.00   29
  6  \w    -23.00   7.00   1.00    1.00    --    0.00  57.00 -30.00   30
  7  \w     54.00  88.00   1.00    1.00    --    0.00  38.00 -90.00   34
  8  \w     49.00  74.00   1.00    1.00    --    0.00  38.00 120.00   25
  9  \w     53.00  88.00   1.00    1.00    --    0.00  57.00 -90.00   35
 10  \w     -3.00  23.00   1.00    1.00    --    0.00  57.00 -90.00   26
 11  \w    -19.00  29.00   1.00    1.00    --    0.00  57.00-150.00   48
 12  \w      8.00  34.00   1.00    1.00    --    0.00  57.00 120.00   26
 13  \w     34.00  84.00   1.00    1.00    --    0.00  57.00-150.00   50
 14  \w     15.00  81.00   1.00    1.00    --    0.00  57.00 -30.00   66
 15  \w    -23.00  21.00   1.00    1.00    --    0.00 -57.00-150.00   44
 16  \w    -86.00 -42.00   1.00    1.00    --    0.00 -57.00-150.00   44
 17  \w     75.00 140.00   1.00    1.00    --   95.80  45.00 -90.00   65
 18  \w     73.00 184.00   1.00    1.00    --   95.80  61.00  90.00  111
 19  \w     71.00 104.00   1.00    1.00    --   95.80  61.00 -60.00   33
 20  \w     58.00 117.00   1.00    1.00    --   95.80 -82.00  90.00   59
 21  \w     63.00  89.00   1.00    1.00    --   95.80  82.00   0.00   26
 22  \w     48.00 127.00   1.00    1.00    --   95.80 -82.00-120.00   79
 23  \w     67.00 122.00   1.00    1.00    --   95.80  72.00 -59.14   55
 24  \w    125.00 185.00   1.00    1.00    --   95.80  81.00  17.93   60
 25  \w     71.00 135.00   1.00    1.00    --   95.80  61.00-180.00   64
 26  \w     65.00 107.00   1.00    1.00    --   95.80  77.00  90.00   42
 27  \w     65.00  96.00   1.00    1.00    --   95.80  77.00-150.00   31
 28  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  60.00   25
 29  \w    116.00 142.00   1.00    1.00    --   95.80  77.00  60.00   26
 30  \w     41.00 116.00   1.00    1.00    --   95.80 -77.00-180.00   75
 31  \w    119.00 185.00   1.00    1.00    --   95.80  61.00 -90.00   66
 32  \w     72.00  97.00   1.00    1.00    --   95.80  61.00 -90.00   25
 33  \w      7.00  33.00   1.00    1.00    --   95.80 -82.00-120.00   26
 34  \w     65.00 100.00   1.00    1.00    --   95.80  77.00-180.00   35
 35  \w     70.00 127.00   1.00    1.00    --   95.80 -82.00 -60.00   57
 36  \w    115.00 185.00   1.00    1.00    --   95.80  45.00-120.00   70
 37  \w    133.00 166.00   1.00    1.00    --   95.80  71.00 -30.14   33
 38  \w    104.00 184.00   1.00    1.00    --   95.80  82.00 -30.00   80
 39  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-180.00   25
 40  \w     66.00  92.00   1.00    1.00    --   95.80  77.00   0.00   26
 41  \w     66.00  92.00   1.00    1.00    --   95.80  77.00 120.00   26
 42  \w    130.00 171.00   1.00    1.00    --   95.80  77.00 120.00   41
 43  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-150.00   25
 44  \w     76.00 102.00   1.00    1.00    --   95.80  45.00 -60.00   26
 45  \w    136.00 185.00   1.00    1.00    --   95.80  45.00 -60.00   49
 46  \w     65.00  92.00   1.00    1.00    --   95.80  77.00 150.00   27
 47  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -30.00   26
 48  \w     12.00  48.00   1.00    1.00    --   95.80 -82.00 -60.00   36
 49  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -60.00   25
 50  \w     75.00 107.00   1.00    1.00    --   95.80  45.00-120.00   32
 51  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  30.00   25
 52  \w     73.00 123.00   1.00    1.00    --   95.80  61.00  60.00   50
 53  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 54  \w     63.00  98.00   1.00    1.00    --   95.80  82.00 120.00   35
 55  \w     72.00 105.00   1.00    1.00    --   95.80 -82.00 -90.00   33
 56  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-120.00   25
 57  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 58  \w     71.00 182.00   1.00    1.00    --   95.80  61.00   0.00  111
 59  \w      7.00 113.00   1.00    1.00    --   95.80 -61.00  30.00  106
 60  \w     67.00  97.00   1.00    1.00    --   95.80  71.00 -30.14   30
 61  \w     63.00  89.00   1.00    1.00    --   95.80  81.00  17.93   26
 62  \w      9.00  72.00   1.00    1.00    --   95.80 -82.00  30.00   63
 63  \w     79.00 107.00   1.00    1.00    --   95.80 -82.00  30.00   28
 64  \w     66.00 185.00   1.00    1.00    --   95.80  75.00 108.86  119
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0887546000
_diffrn_orient_matrix_UB_12      0.0320459000
_diffrn_orient_matrix_UB_13      -0.0718209000
_diffrn_orient_matrix_UB_21      0.1783939000
_diffrn_orient_matrix_UB_22      0.0194331000
_diffrn_orient_matrix_UB_23      0.0552932000
_diffrn_orient_matrix_UB_31      -0.0119652000
_diffrn_orient_matrix_UB_32      -0.1842170000
_diffrn_orient_matrix_UB_33      -0.0259457000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            23454
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.590
_diffrn_reflns_theta_min         5.398
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.696
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.16212
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.378
_exptl_crystal_description       block
_exptl_crystal_F_000             476
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.46
_exptl_crystal_size_min          0.42
_refine_diff_density_max         0.253
_refine_diff_density_min         -0.385
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.0075(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         4381
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0496P)^2^+0.2718P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1060
_refine_ls_wR_factor_ref         0.1080
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4015
_reflns_number_total             4381
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00577c2.cif
_cod_data_source_block           exp_588
_cod_database_code               1554949
_shelx_shelxl_version_number     2016/6
_reflns_odcompleteness_completeness 99.57
_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, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24)
2.b X=CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C25(H25A,H25B,H25C)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              97611
_shelx_hkl_checksum              46354
_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 7.646
_oxdiff_exptl_absorpt_empirical_full_min 0.398