N-Heterocyclic Carbene-Catalyzed β-Addition of Enals to 3-Alkylenyloxindoles: Synthesis of Oxindoles with All-Carbon Quaternary Stereocenters
Zhang, Chun-Lin; Han, You-Feng; Ye, Song; Chemical Communications  (2019) –; doi:10.1039/C9CC03099A

data_7123652
_publ_section_title
;
 N-Heterocyclic Carbene-Catalyzed \b-Addition of Enals to
 3-Alkylenyloxindoles: Synthesis of Oxindoles with All-Carbon Quaternary
 Stereocenters
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03099A
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H26 Br N3 O6'
_chemical_formula_sum            'C30 H26 Br N3 O6'
_chemical_formula_weight         604.45
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-01-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-01 deposited with the CCDC.    2019-06-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.9640(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.07780(10)
_cell_length_b                   9.43960(10)
_cell_length_c                   13.27380(10)
_cell_measurement_reflns_used    29233
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      75.2070
_cell_measurement_theta_min      3.5530
_cell_volume                     1413.17(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14e (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_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    0.80    --   47.20  75.00 -91.00  190
  2  \w     81.00 169.00   0.50    1.00    --  103.25  75.00 -91.00  176
  3  \w     91.00 169.00   0.50    1.00    --  103.25  30.00  30.00  156
  4  \w     35.00 120.00   0.50    0.80    --   47.20  38.00  30.00  170
  5  \w     31.00 125.00   0.50    1.00    --  103.25 -75.00 141.00  188
  6  \w     32.00 116.00   0.50    1.00    --  103.25 -45.00 150.00  168
  7  \w     32.00 116.00   0.50    1.00    --  103.25 -45.00 120.00  168
  8  \w     25.00 120.00   0.50    0.80    --   47.20  77.00   0.00  190
  9  \w     32.00 116.00   0.50    1.00    --  103.25 -45.00 -90.00  168
 10  \w     25.00 120.00   0.50    0.80    --   47.20  77.00  60.00  190
 11  \w     25.00 120.00   0.50    0.80    --   47.20  77.00 -60.00  190
 12  \w     25.00 120.00   0.50    0.80    --   47.20  77.00-180.00  190
 13  \w     32.00 120.00   0.50    0.80    --   47.20  57.00 -90.00  176
 14  \w     31.00 109.00   0.50    1.00    --  103.25 -94.00 -30.00  156
 15  \w     31.00 117.00   0.50    1.00    --  103.25-125.00 120.00  172
 16  \w     16.00  95.00   0.50    0.80    --   47.20-125.00 120.00  158
 17  \w    -24.00  69.00   0.50    0.80    --   47.20 -75.00 141.00  186
 18  \w     32.00 120.00   0.50    0.80    --   47.20  57.00 150.00  176
 19  \w     16.00  95.00   0.50    0.80    --   47.20-125.00-180.00  158
 20  \w    -69.00  26.00   0.50    0.80    --  -47.20  75.00 -91.00  190
 21  \w   -112.00 -24.00   0.50    1.00    --  -99.00  30.00  60.00  176
 22  \w   -121.00 -26.00   0.50    1.00    --  -99.00  75.00 -91.00  190
 23  \w   -120.00 -25.00   0.50    0.80    --  -47.20 -75.00 141.00  190
 24  \w   -120.00 -71.00   0.50    0.80    --  -47.20-125.00 -90.00   98
 25  \w   -168.00 -86.00   0.50    1.00    --  -99.00 -45.00  90.00  164
 26  \w   -168.00 -77.00   0.50    1.00    --  -99.00 -75.00 141.00  182
 27  \w   -168.00 -85.00   0.50    1.00    --  -99.00 -15.00  30.00  166
 28  \w   -168.00 -86.00   0.50    1.00    --  -99.00 -30.00   0.00  164
 29  \w   -168.00 -81.00   0.50    1.00    --  -99.00 -94.00 -90.00  174
 30  \w   -168.00 -86.00   0.50    1.00    --  -99.00 -45.00-180.00  164
 31  \w   -168.00 -86.00   0.50    1.00    --  -99.00 -45.00-150.00  164
 32  \w   -168.00 -86.00   0.50    1.00    --  -99.00 -30.00 -30.00  164
 33  \w   -168.00 -94.00   0.50    1.00    --  -99.00 -61.00  60.00  148
 34  \w   -168.00 -86.00   0.50    1.00    --  -99.00 -45.00 150.00  164
 35  \w   -168.00 -76.00   0.50    1.00    --  -99.00 -77.00 -30.00  184
 36  \w   -168.00 -76.00   0.50    1.00    --  -99.00 -77.00 -90.00  184
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0112892000
_diffrn_orient_matrix_UB_12      0.1215401000
_diffrn_orient_matrix_UB_13      0.0731374000
_diffrn_orient_matrix_UB_21      0.1224634000
_diffrn_orient_matrix_UB_22      0.0561927000
_diffrn_orient_matrix_UB_23      0.0078340000
_diffrn_orient_matrix_UB_31      -0.0591742000
_diffrn_orient_matrix_UB_32      0.0933139000
_diffrn_orient_matrix_UB_33      -0.1002904000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0127
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            30640
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.360
_diffrn_reflns_theta_min         3.566
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.386
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88633
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            white
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_description       needle
_exptl_crystal_F_000             620
_exptl_crystal_size_max          0.175
_exptl_crystal_size_mid          0.032
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.263
_refine_diff_density_min         -0.373
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 2493 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.019(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     391
_refine_ls_number_reflns         5656
_refine_ls_number_restraints     109
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0257
_refine_ls_R_factor_gt           0.0250
_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^)+(0.0353P)^2^+0.4245P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0666
_refine_ls_wR_factor_ref         0.0678
_reflns_Friedel_coverage         0.848
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.947
_reflns_number_gt                5555
_reflns_number_total             5656
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03099a2.cif
_cod_data_source_block           tx255
_cod_database_code               7123652
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         CHNOBr
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1A-C18 = N1-C18
 1.47 with sigma of 0.01
 O3A-N1A = O3-N1 = O4A-N1A = O4-N1
 1.22 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O3 \\sim O4 \\sim N1 \\sim N1A \\sim O3A \\sim O4A: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.04
Uanis(O3) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(N1A) \\sim
Ueq, Uanis(O3A) \\sim Ueq, Uanis(O4A) \\sim Ueq: with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Others
 Sof(N1A)=Sof(O3A)=Sof(O4A)=1-FVAR(1)
 Sof(O3)=Sof(O4)=Sof(N1)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C21(H21)
5.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C16(H16A,H16B), C28(H28A,H28B)
5.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15), C22(H22), C23(H23), C25(H25), C26(H26)
5.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              4171
_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 1.451
_oxdiff_exptl_absorpt_empirical_full_min 0.740