A tandem dearomatization/rearomatization strategy: enantioselective N-heterocyclic carbene-catalyzed α-arylation
Wu, Zijun; Wang, Jian; Chemical Science  (2019) –; doi:10.1039/C8SC04601H

data_1550480
_publ_section_title
;
 A tandem dearomatization/rearomatization strategy: enantioselective
 N-heterocyclic carbene-catalyzed \a-arylation
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC04601H
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C17 H17 Cl N2 O3'
_chemical_formula_sum            'C17 H17 Cl N2 O3'
_chemical_formula_weight         332.77
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2018-07-27 deposited with the CCDC.
2018-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.1000(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.59900(10)
_cell_length_b                   10.24900(10)
_cell_length_c                   10.48800(10)
_cell_measurement_reflns_used    9866
_cell_measurement_temperature    100.3(7)
_cell_measurement_theta_max      71.1000
_cell_measurement_theta_min      4.2780
_cell_volume                     771.861(15)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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_environment      N~2~
_diffrn_ambient_temperature      100.3(7)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2137
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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    -40.00 -13.00   1.00    1.00    --  -40.81 -57.00  90.00   27
  2  \w   -113.00 -41.00   1.00    1.00    --  -40.81 -57.00  90.00   72
  3  \w    -72.00   4.00   1.00    1.00    --  -40.81  77.00  30.00   76
  4  \w     10.00  35.00   1.00    1.00    --  -40.81  77.00  30.00   25
  5  \w     20.00 108.00   1.00    1.00    --  100.91 -95.00-150.00   88
  6  \w     82.00 173.00   1.00    1.00    --  100.91  61.00   0.00   91
  7  \w     31.00 114.00   1.00    1.00    --  100.91 -45.00-150.00   83
  8  \w    115.00 166.00   1.00    1.00    --  100.91 125.00 -90.00   51
  9  \w    119.00 170.00   1.00    1.00    --  100.91  15.00 -30.00   51
 10  \w    -60.00  27.00   1.00    1.00    --  -40.81  57.00-120.00   87
 11  \w     38.00 106.00   1.00    1.00    --   40.81  38.00 -30.00   68
 12  \w     81.00 113.00   1.00    1.00    --  100.29-125.00 -30.00   32
 13  \w     76.00 159.00   1.00    1.00    --  100.29  45.00  60.00   83
 14  \w     69.00 117.00   1.00    1.00    --  100.29-125.00 150.00   48
 15  \w     62.00 120.00   1.00    1.00    --  100.29 -30.00   0.00   58
 16  \w     98.00 124.00   1.00    1.00    --  100.29 125.00  60.00   26
 17  \w     30.00 125.00   1.00    1.00    --  100.29 -77.00 -30.00   95
 18  \w    -44.00 -13.00   1.00    1.00    --  -40.81 -57.00 -90.00   31
 19  \w   -108.00 -67.00   1.00    1.00    --  -40.81 -57.00 -90.00   41
 20  \w     65.00  97.00   1.00    1.00    --   40.81-125.00 -90.00   32
 21  \w      8.00  33.00   1.00    1.00    --   42.00  82.00  94.18   25
 22  \w     11.00  37.00   1.00    1.00    --   46.00  84.00 -39.89   26
 23  \w     16.00  44.00   1.00    1.00    --   50.00  81.00 147.30   28
 24  \w     17.00  42.00   1.00    1.00    --   50.00  80.00-141.21   25
 25  \w     27.00  53.00   1.00    1.00    --   58.00  76.00  19.51   26
 26  \w     29.00  61.00   1.00    1.00    --   58.00  76.00 114.13   32
 27  \w     89.00 115.00   1.00    1.00    --   58.00  76.00 114.13   26
 28  \w     32.00  70.00   1.00    1.00    --   62.00  75.00-174.21   38
 29  \w    102.00 129.00   1.00    1.00    --   62.00  75.00-174.21   27
 30  \w     32.00  58.00   1.00    1.00    --   62.00  77.00 -41.44   26
 31  \w     36.00  64.00   1.00    1.00    --   62.00  76.00 131.53   28
 32  \w    113.00 138.00   1.00    1.00    --   62.00  76.00-108.38   25
 33  \w     30.00  59.00   1.00    1.00    --   62.00  76.00-108.38   29
 34  \w     34.00  60.00   1.00    1.00    --   66.00  75.00 -77.68   26
 35  \w     33.00  74.00   1.00    1.00    --   66.00  77.00  46.42   41
 36  \w    111.00 137.00   1.00    1.00    --   66.00  75.00 -77.68   26
 37  \w     47.00  73.00   1.00    1.00    --   78.00  71.00 -29.61   26
 38  \w     68.00 144.00   1.00    1.00    --  100.29  77.00 120.00   76
 39  \w     81.00 164.00   1.00    1.00    --  100.29  61.00-150.00   83
 40  \w     68.00 130.00   1.00    1.00    --  100.29  77.00 -90.00   62
 41  \w     68.00  94.00   1.00    1.00    --  100.29  77.00 -60.00   26
 42  \w     69.00  95.00   1.00    1.00    --  100.29  77.00   0.00   26
 43  \w     69.00 120.00   1.00    1.00    --  100.29  77.00  90.00   51
 44  \w     68.00  94.00   1.00    1.00    --  100.29  77.00  30.00   26
 45  \w     69.00 120.00   1.00    1.00    --  100.29  77.00-120.00   51
 46  \w    145.00 171.00   1.00    1.00    --  100.29  77.00-180.00   26
 47  \w     68.00  94.00   1.00    1.00    --  100.29  77.00-180.00   26
 48  \w     68.00  94.00   1.00    1.00    --  100.29  77.00 -30.00   26
 49  \w     73.00  99.00   1.00    1.00    --  100.29  61.00-120.00   26
 50  \w    101.00 164.00   1.00    1.00    --  100.29  77.00 150.00   63
 51  \w     70.00  96.00   1.00    1.00    --  100.29  77.00  60.00   26
 52  \w     68.00  96.00   1.00    1.00    --  100.29  77.00 150.00   28
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1979109000
_diffrn_orient_matrix_UB_12      -0.0532133000
_diffrn_orient_matrix_UB_13      0.0245912000
_diffrn_orient_matrix_UB_21      -0.0059431000
_diffrn_orient_matrix_UB_22      0.0499623000
_diffrn_orient_matrix_UB_23      -0.1398756000
_diffrn_orient_matrix_UB_31      0.0825344000
_diffrn_orient_matrix_UB_32      0.1314178000
_diffrn_orient_matrix_UB_33      0.0632272000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0242
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            11126
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.200
_diffrn_reflns_theta_min         4.461
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.342
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81086
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.432
_exptl_crystal_description       block
_exptl_crystal_F_000             348
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.32
_refine_diff_density_max         0.160
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 1352 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         2950
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0245
_refine_ls_R_factor_gt           0.0244
_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^)+(0.0360P)^2^+0.1680P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0628
_refine_ls_wR_factor_ref         0.0629
_reflns_Friedel_coverage         0.864
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                2941
_reflns_number_total             2950
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04601h2.cif
_cod_data_source_block           20180723wuzijun
_cod_database_code               1550480
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_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 Riding coordinates:
 N1(H1)
2.b Ternary CH refined with riding coordinates:
 C11(H11)
2.c Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B)
2.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8)
2.e Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C)
;
_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 1.408
_oxdiff_exptl_absorpt_empirical_full_min 0.765