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_1574407
_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 Br N'
_chemical_formula_sum            'C10 H8 Br N'
_chemical_formula_weight         222.08
_chemical_name_systematic
(1R,2R)-2-bromo-2-phenylcyclopropane-1-carbonitrile
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-04-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-20 deposited with the CCDC.	2025-03-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.0173(4)
_cell_length_b                   9.8390(6)
_cell_length_c                   12.9563(8)
_cell_measurement_reflns_used    8683
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.73
_cell_measurement_theta_min      5.94
_cell_volume                     894.54(9)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0781
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20294
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         71.122
_diffrn_reflns_theta_min         4.910
_diffrn_source_current           3.57
_diffrn_source_power             0.24947159999999996
_diffrn_source_voltage           69.88
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.812
_exptl_absorpt_correction_T_max  0.7534
_exptl_absorpt_correction_T_min  0.6502
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1528 before and 0.0758 after correction.
The Ratio of minimum to maximum transmission is 0.8630.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.649
_exptl_crystal_description       bulk
_exptl_crystal_F_000             440
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.558
_refine_diff_density_min         -0.560
_refine_diff_density_rms         0.112
_refine_ls_abs_structure_details
;
 Flack x determined using 872 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_coef       0.0015(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.120
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     110
_refine_ls_number_reflns         2614
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0154P)^2^+0.2469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0560
_refine_ls_wR_factor_ref         0.0586
_reflns_Friedel_coverage         0.720
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                2285
_reflns_number_total             2614
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00461f2.cif
_cod_data_source_block           20230327alphabr_0m_a
_cod_depositor_comments
'Adding full bibliography for 1574403--1574407.cif.'
_cod_database_code               1574407
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.702
_shelx_estimated_absorpt_t_min   0.516
_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)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C9(H9), C10(H10)
;
_olex2_submission_special_instructions 'No special instructions were received'