Chiral iron porphyrin (+)-D4-(por)FeCl catalyzes highly enantioselective cyclopropanation of alkenes using in situ generated diazoacetonitrile with up to 35 000 product turnover
Tan, Hao-Chong; Shing, Ka-Pan; Wang, Hua-Hua; Liu, Yungen; Che, Chi-Ming; Chemical Science 16 (2025) 7191–7202; doi:10.1039/D5SC00461F

data_1574404
_publ_section_title
;
 Chiral iron porphyrin (+)-D4-(por)FeCl catalyzes highly enantioselective
 cyclopropanation of alkenes using in situ generated diazoacetonitrile
 with up to 35&#x2009;000 product turnover
;
_journal_issue                   17
_journal_name_full               'Chemical Science'
_journal_page_first              7191
_journal_page_last               7202
_journal_paper_doi               10.1039/D5SC00461F
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C10 H8 N2 O2'
_chemical_formula_sum            'C10 H8 N2 O2'
_chemical_formula_weight         188.18
_chemical_name_systematic
(1S,2S)-2-(4-nitrophenyl)cyclopropane-1-carbonitrile
_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   geom
_audit_creation_date             2023-10-30
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-04-20 deposited with the CCDC.	2025-03-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.797(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2102(14)
_cell_length_b                   6.6977(10)
_cell_length_c                   14.702(2)
_cell_measurement_reflns_used    9439
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      64.96
_cell_measurement_theta_min      4.23
_cell_volume                     896.3(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT 2014'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker PHOTON III area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0538
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            20517
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         60.562
_diffrn_reflns_theta_min         2.646
_diffrn_source                   'microfocus Metaljet'
_diffrn_source_current           3.57
_diffrn_source_power             0.24947159999999996
_diffrn_source_type              'Incoatec Metaljet'
_diffrn_source_voltage           69.88
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.528
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6516
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1665 before and 0.0797 after correction.
The Ratio of minimum to maximum transmission is 0.8658.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.395
_exptl_crystal_description       bulk
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.325
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.065
_refine_ls_abs_structure_details
;
 Flack x determined using 1752 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     253
_refine_ls_number_reflns         3991
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0396
_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^)+(0.0701P)^2^+0.1148P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1060
_refine_ls_wR_factor_ref         0.1064
_reflns_Friedel_coverage         0.821
_reflns_Friedel_fraction_full    0.948
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                3941
_reflns_number_total             3991
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00461f2.cif
_cod_data_source_block           20231028thc_4no2cn_0m_a
_cod_depositor_comments
;

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel

 Adding full bibliography for 1574403--1574407.cif.
;
_cod_original_formula_moiety     '2(C10 H8 N2 O2)'
_cod_original_formula_sum        'C20 H16 N4 O4'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     376.37
_cod_database_code               1574404
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.902
_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:
 C2(H2), C3(H3), C13(H13), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C9(H9), C10(H10), C16(H16), C17(H17), C21(H21), C22(H22)
;
_shelx_res_checksum              39637
_olex2_submission_special_instructions 'No special instructions were received'