Asymmetric synthesis of pharmaceutically relevant 1-aryl-2-heteroaryl- and 1,2-diheteroarylcyclopropane-1-carboxylates
Sharland, Jack C.; Wei, Bo; Hardee, David J.; Hodges, Timothy R.; Gong, Wei; Voight, Eric A.; Davies, Huw M. L.; Chemical Science  (2021) –; doi:10.1039/D1SC02474D

data_1564262
_publ_section_title
;
 Asymmetric synthesis of pharmaceutically relevant 1-aryl-2-heteroaryl-
 and 1,2-diheteroarylcyclopropane-1-carboxylates
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02474D
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H12 Br Cl4 N O2'
_chemical_formula_sum            'C17 H12 Br Cl4 N O2'
_chemical_formula_weight         484.004
_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_Int_Tables_number      4
_audit_creation_date             2020-08-25
_audit_creation_method
;
Olex2 1.3-dev
(compiled 2020.07.30 svn.rde3f2a17 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-03-17 deposited with the CCDC.	2021-06-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.220(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.95245(14)
_cell_length_b                   9.2860(2)
_cell_length_c                   16.6609(4)
_cell_measurement_reflns_used    18563
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      37.5020
_cell_measurement_theta_min      2.4440
_cell_volume                     915.50(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3-dev (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9994
_diffrn_measured_fraction_theta_max 0.9605
_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    -47.00  39.00   0.50    3.40    --   25.84 -57.00  90.00  172
  2  \w     33.00  64.00   0.50    3.40    --   25.84-115.00  48.00   62
  3  \w     22.00  48.00   0.50    3.40    --   25.84 -77.00 -90.00   52
  4  \w     31.00  56.00   0.50    3.40    --   25.84 -99.00-180.00   50
  5  \w     73.00 102.00   0.50    3.40    --   25.84-169.00 -95.00   58
  6  \w    -17.00  19.00   0.50    3.40    --   25.84 -19.00  90.00   72
  7  \w    -23.00  60.00   0.50    3.40    --   25.84 -99.00  90.00  166
  8  \w    -48.00  19.00   0.50    3.40    --   25.84 -19.00 150.00  134
  9  \w     24.00  86.00   0.50    3.40    --   25.84  77.00 150.00  124
 10  \w     53.00  79.00   0.50    3.40    --   25.84  77.00  60.00   52
 11  \w     48.00  73.00   0.50    3.40    --   25.84 169.00 -78.00   50
 12  \w    -49.00  19.00   0.50    3.40    --   25.84 -19.00 -30.00  136
 13  \w    -42.00  -2.00   0.50    3.40    --   25.84 -77.00 -90.00   80
 14  \w    -20.00   5.00   0.50    3.40    --   25.84 -99.00-180.00   50
 15  \w     20.00  46.00   0.50    3.40    --   25.84  77.00  60.00   52
 16  \w     42.00  88.00   0.50    3.40    --   25.84 178.00   0.00   92
 17  \w    -88.00  -6.00   0.50    3.40    --  -25.84 -77.00  90.00  164
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0445111000
_diffrn_orient_matrix_UB_12      -0.0037982000
_diffrn_orient_matrix_UB_13      0.0377638000
_diffrn_orient_matrix_UB_21      -0.0205703000
_diffrn_orient_matrix_UB_22      0.0752309000
_diffrn_orient_matrix_UB_23      -0.0014109000
_diffrn_orient_matrix_UB_31      -0.1093318000
_diffrn_orient_matrix_UB_32      -0.0125960000
_diffrn_orient_matrix_UB_33      -0.0201908000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_Laue_measured_fraction_full 0.9994
_diffrn_reflns_Laue_measured_fraction_max 0.9605
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            29643
_diffrn_reflns_point_group_measured_fraction_full 0.9997
_diffrn_reflns_point_group_measured_fraction_max 0.9425
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         38.07
_diffrn_reflns_theta_min         2.46
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.840
_exptl_absorpt_correction_T_max  0.645
_exptl_absorpt_correction_T_min  0.529
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.756
_exptl_crystal_description       prism
_exptl_crystal_F_000             480.521
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.327
_exptl_crystal_size_mid          0.278
_exptl_crystal_size_min          0.219
_refine_diff_density_max         0.5379
_refine_diff_density_min         -0.4013
_refine_diff_density_rms         0.0826
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.015(3)
_refine_ls_d_res_high            0.5763
_refine_ls_d_res_low             8.2814
_refine_ls_goodness_of_fit_ref   0.9915
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    2
_refine_ls_number_parameters     347
_refine_ls_number_reflns         9440
_refine_ls_number_restraints     40
_refine_ls_restrained_S_all      0.9894
_refine_ls_R_factor_all          0.0288
_refine_ls_R_factor_gt           0.0244
_refine_ls_shift/su_max          0.0040
_refine_ls_shift/su_mean         0.0002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0257P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0500
_refine_ls_wR_factor_ref         0.0510
_reflns_Friedel_coverage         0.923
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              15
_reflns_limit_k_min              -15
_reflns_limit_l_max              28
_reflns_limit_l_min              -28
_reflns_number_gt                8716
_reflns_number_total             9440
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d1sc02474d2.cif
_cod_data_source_block           JCS-24-8-2020_Mo
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               1564262
_chemical_oxdiff_formula         'C34  H24  Br2  Cl8  N2  O4  '
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     36.23
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(H14) = Uanis(H13)
Uanis(H17) = Uanis(H16)
2. Rigid body (RIGU) restrains
 C10, H10a
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C14, H14
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C13, H13
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C16, H16
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 H3, C3
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C17, H17
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 H10a, C10
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2, H2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C5, H5
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 H6, C6
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C10, H10b
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 H8b, C8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 H8a, C8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone'
_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 1.329
_oxdiff_exptl_absorpt_empirical_full_min 0.770