Asymmetric Formal [5 + 3] Cycloadditions with Unmodified Morita–Baylis–Hillman Alcohols via Double Activation Catalysis
Yang, Qian-Qian; Yin, Xiang; He, Xiao-Long; Du, Wei; Chen, Ying-Chun; ACS Catalysis 9 (2019) 1258–; doi:10.1021/acscatal.8b04942

data_4514754
_publ_section_title
;
 Asymmetric Formal [5 + 3] Cycloadditions with Unmodified
 Morita--Baylis--Hillman Alcohols via Double Activation Catalysis
;
_journal_issue                   2
_journal_name_full               'ACS Catalysis'
_journal_page_first              1258
_journal_paper_doi               10.1021/acscatal.8b04942
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H30 N4 O2, C H2 Cl2'
_chemical_formula_sum            'C36 H32 Cl2 N4 O2'
_chemical_formula_weight         623.55
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2018-12-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.0958(16)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.3963(2)
_cell_length_b                   10.25731(18)
_cell_length_c                   13.2680(2)
_cell_measurement_reflns_used    3970
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.9430
_cell_measurement_theta_min      3.8890
_cell_volume                     1544.84(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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   -104.00 -20.00   1.00    1.00    --  -36.42 -57.00-150.00   84
  2  \w    -53.00  31.00   1.00    1.00    --  -36.42  57.00   0.00   84
  3  \w     10.00 104.00   1.00    1.00    --   36.42  77.00  30.00   94
  4  \w     20.00 104.00   1.00    1.00    --   36.42  57.00 150.00   84
  5  \w     39.00 109.00   1.00    3.62    --  108.71 -94.00 120.00   70
  6  \w     91.00 176.00   1.00    3.62    --  108.71  61.00  90.00   85
  7  \w     87.00 178.00   1.00    3.62    --  108.71  30.00  60.00   91
  8  \w     40.00 126.00   1.00    3.62    --  108.71 -45.00 -30.00   86
  9  \w     39.00 109.00   1.00    3.62    --  108.71 -94.00-120.00   70
 10  \w     39.00 109.00   1.00    3.62    --  108.71 -94.00   0.00   70
 11  \w     91.00 177.00   1.00    3.62    --  108.71  45.00 150.00   86
 12  \w     70.00 178.00   1.00    3.62    --  108.71  15.00  30.00  108
 13  \w     40.00 126.00   1.00    3.62    --  108.71 -45.00  90.00   86
 14  \w    -55.00  33.00   1.00    1.00    --  -36.42  38.00-180.00   88
 15  \w      1.00  51.00   1.00    1.00    --   36.42 -99.00-120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0671571000
_diffrn_orient_matrix_UB_12      0.0607298000
_diffrn_orient_matrix_UB_13      0.0943285000
_diffrn_orient_matrix_UB_21      -0.1178068000
_diffrn_orient_matrix_UB_22      0.0388858000
_diffrn_orient_matrix_UB_23      0.0400471000
_diffrn_orient_matrix_UB_31      -0.0038241000
_diffrn_orient_matrix_UB_32      -0.1318931000
_diffrn_orient_matrix_UB_33      0.0554631000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0391
_diffrn_reflns_av_unetI/netI     0.0536
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            9236
_diffrn_reflns_point_group_measured_fraction_full 0.791
_diffrn_reflns_point_group_measured_fraction_max 0.771
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.896
_diffrn_reflns_theta_min         3.894
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.206
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60908
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.341
_exptl_crystal_description       needle
_exptl_crystal_F_000             652
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.658
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 1382 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.014(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     397
_refine_ls_number_reflns         4746
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0597
_refine_ls_R_factor_gt           0.0578
_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^)+(0.1139P)^2^+0.2735P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1513
_refine_ls_wR_factor_ref         0.1547
_reflns_Friedel_coverage         0.474
_reflns_Friedel_fraction_full    0.557
_reflns_Friedel_fraction_max     0.527
_reflns_number_gt                4544
_reflns_number_total             4746
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04942_si_003.cif
_cod_data_source_block           6
_cod_original_cell_volume        1544.85(5)
_cod_database_code               4514754
_reflns_odcompleteness_completeness 99.93
_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
2.a Ternary CH refined with riding coordinates:
 C00I(H00I), C00J(H00J), C00M(H00M), C00Q(H00Q)
2.b Secondary CH2 refined with riding coordinates:
 C00H(H00A,H00B), C00S(H00C,H00D), C00U(H00E,H00G), C018(H01A,H01B)
2.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00F(H00F), C00K(H00K), C00N(H00N), C00P(H00P), C00R(H00R),
 C00T(H00T), C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z),
 C010(H010), C011(H011), C012(H012), C013(H013), C014(H014), C015(H015),
 C016(H016), C017(H017)
;
_shelx_res_checksum              10069
_shelx_hkl_checksum              56247
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2018-12-06
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.642
_oxdiff_exptl_absorpt_empirical_full_min 0.717