Stereoselective palladium-catalyzed carboetherification of cyclopropenes <i>via</i> a tethering strategy.
Brownsey, Duncan K.; Schoepfer, Alexandre A.; Waser, Jerome; Chemical science 17 (2026) 5072–5078; doi:10.1039/d5sc09351a

data_1576855
_publ_section_title
;
 Stereoselective palladium-catalyzed carboetherification of cyclopropenes
 <i>via</i> a tethering strategy.
;
_journal_issue                   10
_journal_name_full               'Chemical science'
_journal_page_first              5072
_journal_page_last               5078
_journal_paper_doi               10.1039/d5sc09351a
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C21 H17 F6 N O3'
_chemical_formula_sum            'C21 H17 F6 N O3'
_chemical_formula_weight         445.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-05-05
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-05-16 deposited with the CCDC.	2026-01-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.3773(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.77504(10)
_cell_length_b                   24.62736(17)
_cell_length_c                   11.15008(6)
_cell_measurement_reflns_used    37169
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.0720
_cell_measurement_theta_min      2.9840
_cell_volume                     4057.09(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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     89.00 117.00   0.50    0.20    --   79.75  21.00  17.60   56
  2  \w     65.00  95.00   0.50    0.20    --   79.75  20.00  -9.50   60
  3  \w     58.00  94.00   0.50    0.20    --   79.75  20.00 -45.66   72
  4  \w     77.00 103.00   0.50    0.20    --   79.75  23.00 -92.89   52
  5  \w     64.00  89.00   0.50    0.20    --   79.75  21.00-102.48   50
  6  \w     46.00 108.00   0.50    0.20    --   79.75   9.00-132.22  124
  7  \w     51.00  76.00   0.50    0.20    --   76.61  15.00   0.00   50
  8  \w     46.00  92.00   0.50    0.20    --   79.75   4.00 -46.34   92
  9  \w     86.00 114.00   0.50    0.20    --   76.61  15.00   0.00   56
 10  \w     70.00 119.00   0.50    0.20    --   79.75   7.00  -3.71   98
 11  \w     70.00 111.00   0.50    0.20    --   79.75   8.00  51.81   82
 12  \w     55.00 101.00   0.50    0.20    --   79.75   9.00 153.60   92
 13  \w     46.00  71.00   0.50    0.20    --   79.75 -64.00  -1.15   50
 14  \w     45.00 100.00   0.50    0.20    --   79.75-114.00 -33.51  110
 15  \w     71.00  98.00   0.50    0.20    --   76.61-125.00-180.00   54
 16  \w     39.00  65.00   0.50    0.20    --   75.73-111.00-137.00   52
 17  \w     27.00  81.00   0.50    0.20    --   63.87-111.00-137.00  108
 18  \w     65.00  90.00   0.50    0.20    --   76.61-111.00-137.00   50
 19  \w     77.00 102.00   0.50    0.20    --   76.61-125.00 -90.00   50
 20  \w     43.00  81.00   0.50    0.20    --   76.61 -95.00 -90.00   76
 21  \w     37.00  82.00   0.50    0.20    --   75.73-111.00-120.00   90
 22  \w     45.00  85.00   0.50    0.20    --   76.61 -95.00-120.00   80
 23  \w     78.00 103.00   0.50    0.20    --   76.61-125.00 -60.00   50
 24  \w     39.00  81.00   0.50    0.20    --   76.61 -95.00 -30.00   84
 25  \w     63.00  89.00   0.50    0.20    --   75.73-111.00   0.00   52
 26  \w     48.00  73.00   0.50    0.20    --   76.61 -95.00  60.00   50
 27  \w     51.00  83.00   0.50    0.20    --   76.61 -95.00  30.00   64
 28  \w     46.00  79.00   0.50    0.20    --   76.61 -95.00   0.00   66
 29  \w     26.00  64.00   0.50    0.20    --   63.87 -95.00  60.00   76
 30  \w     78.00 103.00   0.50    0.20    --   76.61-125.00 150.00   50
 31  \w     47.00  72.00   0.50    0.20    --   63.87 -95.00 120.00   50
 32  \w   -111.00 -86.00   0.50    0.20    --  -76.25 -75.00 -90.15   50
 33  \w   -111.00 -85.00   0.50    0.20    --  -76.25 -82.00 -92.48   52
 34  \w   -109.00 -82.00   0.50    0.20    --  -76.25 -81.00-176.69   54
 35  \w   -109.00 -84.00   0.50    0.20    --  -76.25 -87.00 -18.32   50
 36  \w   -112.00 -85.00   0.50    0.20    --  -76.25 -96.00 132.42   54
 37  \w    -71.00 -36.00   0.50    0.20    --  -71.12   0.00 150.00   70
 38  \w    -66.00 -38.00   0.50    0.20    --  -71.12   0.00  90.00   56
 39  \w    -65.00 -34.00   0.50    0.20    --  -71.12   0.00 -60.00   62
 40  \w    -67.00 -42.00   0.50    0.20    --  -71.12   0.00-120.00   50
 41  \w    -84.00 -59.00   0.50    0.20    --  -71.12 111.00 -44.00   50
 42  \w    -71.00 -32.00   0.50    0.20    --  -64.59 111.00 -44.00   78
 43  \w    -67.00 -34.00   0.50    0.20    --  -76.25 136.00-157.16   66
 44  \w    -87.00 -45.00   0.50    0.20    --  -71.12 111.00-120.00   84
 45  \w   -111.00 -78.00   0.50    0.20    --  -76.25 136.00-157.16   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1026749000
_diffrn_orient_matrix_UB_12      -0.0012558000
_diffrn_orient_matrix_UB_13      -0.0232295000
_diffrn_orient_matrix_UB_21      0.0016479000
_diffrn_orient_matrix_UB_22      -0.0612639000
_diffrn_orient_matrix_UB_23      0.0279262000
_diffrn_orient_matrix_UB_31      -0.0182367000
_diffrn_orient_matrix_UB_32      -0.0125799000
_diffrn_orient_matrix_UB_33      -0.1332748000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0170
_diffrn_reflns_av_unetI/netI     0.0110
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            54330
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.363
_diffrn_reflns_theta_min         2.991
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.178
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.591
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on Gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics
as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.458
_exptl_crystal_description       plate
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.290
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.00060(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     570
_refine_ls_number_reflns         8257
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0304
_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^)+(0.0359P)^2^+1.3525P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0768
_refine_ls_wR_factor_ref         0.0786
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7455
_reflns_number_total             8257
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09351a2.cif
_cod_data_source_block           dkb-01-695
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 
;
_cod_original_cell_volume        4057.09(5)
_cod_database_code               1576855
_shelx_shelxl_version_number     2019/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C21 H17 F6 N O3'
_chemical_oxdiff_usercomment     'EtOAc, Toluene, Pentane'
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.757
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C24(H24), C25(H25)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C26(H26A,H26B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16), C18(H18),
 C19(H19), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37),
  C39(H39), C40(H40)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C42(H42A,H42B,H42C)
;
_shelx_res_checksum              15479
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.302
_oxdiff_exptl_absorpt_empirical_full_min 0.720