Kinetic Resolution of 2H-Azirines by Asymmetric Allylation Reactions
Pan, Yu-Liang; Shao, Ying-Bo; Wang, Jie; Liu, Zhen; Chen, Li; Li, Xin; ACS Catalysis  (2021) 13752–13760; doi:10.1021/acscatal.1c03875

data_4519093
_publ_section_title
;
 Kinetic Resolution of 2H-Azirines by Asymmetric Allylation Reactions
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              13752
_journal_page_last               13760
_journal_paper_doi               10.1021/acscatal.1c03875
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H16 Cl N'
_chemical_formula_sum            'C17 H16 Cl N'
_chemical_formula_weight         269.76
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.121(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.6110(6)
_cell_length_b                   9.7776(6)
_cell_length_c                   8.9599(6)
_cell_measurement_reflns_used    4348
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      32.6590
_cell_measurement_theta_min      2.4270
_cell_volume                     728.26(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       CrystalClear(Rigaku,2008)
_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_temperature      113.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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   -115.00  65.00   2.00    3.00    --  -25.00  45.00   0.00   90
  2  \w   -115.00  65.00   2.00    3.00    --  -25.00  45.00  90.00   90
  3  \w   -115.00  65.00   2.00    3.00    --  -25.00  45.00 180.00   90
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Rigaku Saturn 70 CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0773950000
_diffrn_orient_matrix_UB_12      -0.0243736000
_diffrn_orient_matrix_UB_13      -0.0005203000
_diffrn_orient_matrix_UB_21      0.0357927000
_diffrn_orient_matrix_UB_22      0.0533913000
_diffrn_orient_matrix_UB_23      0.0510307000
_diffrn_orient_matrix_UB_31      0.0004514000
_diffrn_orient_matrix_UB_32      -0.0427251000
_diffrn_orient_matrix_UB_33      0.0641473000
_diffrn_radiation_monochromator  confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0401
_diffrn_reflns_av_unetI/netI     0.0477
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            7478
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.450
_diffrn_source                   'rotating anode'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.248
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39663
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)'
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       block
_exptl_crystal_F_000             284
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.139
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1074 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.07(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2952
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0434
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0369P)^2^+0.0556P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0759
_refine_ls_wR_factor_ref         0.0788
_reflns_Friedel_coverage         0.871
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                2662
_reflns_number_total             2952
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c03875_si_002.cif
_cod_data_source_block           r20200710d
_cod_database_code               4519093
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.952
_reflns_odcompleteness_completeness 99.44
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C1-H1A = C1-H1B
 0.95 with sigma of 0.01
 H1B-H1A
 1.55 with sigma of 0.01
 N1-H1
 0.9 with sigma of 0.01
3.a Ternary CH refined with riding coordinates:
 C11(H11)
3.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14),
 C16(H16), C17(H17)
;
_shelx_res_checksum              35114
_shelx_hkl_checksum              96696
_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 2.438
_oxdiff_exptl_absorpt_empirical_full_min 0.569