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_1574405
_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         'C11 H8 F3 N'
_chemical_formula_sum            'C11 H8 F3 N'
_chemical_formula_weight         211.18
_chemical_name_systematic
(1S,2R)-2-phenyl-2-(trifluoromethyl)cyclopropane-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             2024-04-29
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-29 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                   7.1860(6)
_cell_length_b                   10.3981(8)
_cell_length_c                   12.9161(10)
_cell_measurement_reflns_used    9722
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      73.11
_cell_measurement_theta_min      4.75
_cell_volume                     965.10(13)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.989
_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  0.0843
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            19415
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         73.328
_diffrn_reflns_theta_min         4.750
_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    0.703
_exptl_absorpt_correction_T_max  0.7537
_exptl_absorpt_correction_T_min  0.5011
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1558 before and 0.1118 after correction.
The Ratio of minimum to maximum transmission is 0.6649.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.453
_exptl_crystal_description       rod
_exptl_crystal_F_000             432
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.429
_refine_diff_density_min         -0.251
_refine_diff_density_rms         0.076
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.18(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     137
_refine_ls_number_reflns         2901
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0745P)^2^+0.0180P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1063
_refine_ls_wR_factor_ref         0.1077
_reflns_Friedel_coverage         0.725
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                2749
_reflns_number_total             2901
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00461f2.cif
_cod_data_source_block           20230828thc_alphacf3_enantio2__a
_cod_depositor_comments
'Adding full bibliography for 1574403--1574407.cif.'
_cod_database_code               1574405
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.861
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.82(17)
 0.18(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3.a Ternary CH refined with riding coordinates:
 C2(H2)
3.b Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C10(H10), C11(H11)
;
_shelx_res_checksum              74237
_olex2_submission_special_instructions 'No special instructions were received'