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_1576854
_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         'C27 H23 F3 N2 O5'
_chemical_formula_sum            'C27 H23 F3 N2 O5'
_chemical_formula_weight         512.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_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                 110.432(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.4150(5)
_cell_length_b                   9.44890(15)
_cell_length_c                   21.1616(3)
_cell_measurement_reflns_used    13170
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.3340
_cell_measurement_theta_min      3.6900
_cell_volume                     4762.11(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.94a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.94a 64-bit (release 20-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.94a (Rigaku OD, 2023)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.982
_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     61.00 114.00   0.50    0.20    --   79.75  21.00 117.83  106
  2  \w    101.00 127.00   0.50    0.20    --   79.75  22.00 153.37   52
  3  \w     69.00 119.00   0.50    0.20    --   79.75  22.00  30.52  100
  4  \w     84.00 113.00   0.50    0.20    --   79.75   5.00  78.77   58
  5  \w     61.00 126.00   0.50    0.20    --   79.75  17.00   1.27  130
  6  \w     49.00 111.00   0.50    0.20    --   79.75   4.00 167.58  124
  7  \w     49.00  82.00   0.50    0.20    --   79.75  15.00 -18.19   66
  8  \w     51.00 119.00   0.50    0.20    --   76.50  15.00 -90.00  136
  9  \w     62.00 110.00   0.50    0.20    --   79.75  21.00-170.05   96
 10  \w     36.00  61.00   0.50    0.20    --   79.75 -52.00-118.69   50
 11  \w     44.00  70.00   0.50    0.20    --   76.50-125.00 -90.00   52
 12  \w     68.00  93.00   0.50    0.20    --   76.50-125.00-120.00   50
 13  \w     76.00 101.00   0.50    0.20    --   76.50-125.00 -90.00   50
 14  \w     78.00 103.00   0.50    0.20    --   76.50-125.00 -30.00   50
 15  \w     78.00 103.00   0.50    0.20    --   76.50-125.00   0.00   50
 16  \w     59.00  84.00   0.50    0.20    --   76.50 -95.00   0.00   50
 17  \w     29.00  56.00   0.50    0.20    --   63.61 -95.00   0.00   54
 18  \w     39.00  75.00   0.50    0.20    --   75.71 -95.00 -30.00   72
 19  \w     38.00  72.00   0.50    0.20    --   63.61 -95.00-150.00   68
 20  \w     39.00  64.00   0.50    0.20    --   76.50 -95.00-120.00   50
 21  \w     43.00  84.00   0.50    0.20    --   76.50 -95.00 -90.00   82
 22  \w     54.00  82.00   0.50    0.20    --   76.50 -95.00 -60.00   56
 23  \w     41.00  73.00   0.50    0.20    --   76.50 -95.00  30.00   64
 24  \w    -67.00 -40.00   0.50    0.20    --  -64.68   0.00 -30.00   54
 25  \w    -70.00 -43.00   0.50    0.20    --  -71.11   0.00  60.00   54
 26  \w    -72.00 -36.00   0.50    0.20    --  -71.11   0.00   0.00   72
 27  \w    -67.00 -34.00   0.50    0.20    --  -71.11   0.00 -60.00   66
 28  \w    -68.00 -38.00   0.50    0.20    --  -71.11   0.00-150.00   60
 29  \w   -106.00 -80.00   0.50    0.20    --  -76.25 -85.00 -81.27   52
 30  \w   -111.00 -82.00   0.50    0.20    --  -76.25 -87.00  30.99   58
 31  \w    -97.00 -46.00   0.50    0.20    --  -71.11 125.00  30.00  102
 32  \w    -95.00 -40.00   0.50    0.20    --  -71.11 125.00-120.00  110
;
_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      -0.0487025000
_diffrn_orient_matrix_UB_12      0.0459208000
_diffrn_orient_matrix_UB_13      0.0229239000
_diffrn_orient_matrix_UB_21      -0.0290124000
_diffrn_orient_matrix_UB_22      -0.1436591000
_diffrn_orient_matrix_UB_23      -0.0230535000
_diffrn_orient_matrix_UB_31      0.0312077000
_diffrn_orient_matrix_UB_32      -0.0619164000
_diffrn_orient_matrix_UB_33      0.0705201000
_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  0.0349
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            23714
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.535
_diffrn_reflns_theta_min         3.712
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.975
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.904
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.94a (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    1.430
_exptl_crystal_description       prism
_exptl_crystal_F_000             2128
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.390
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     335
_refine_ls_number_reflns         4842
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0574P)^2^+3.0579P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1062
_refine_ls_wR_factor_ref         0.1121
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3952
_reflns_number_total             4842
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09351a2.cif
_cod_data_source_block           dkb-01-247
_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_database_code               1576854
_shelx_shelxl_version_number     2019/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C27 H23 F3 N2 O5'
_shelx_estimated_absorpt_t_max   0.953
_shelx_estimated_absorpt_t_min   0.884
_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), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19), C23(H23), C24(H24), C26(H26), C27(H27)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C)
;
_shelx_res_checksum              21891
_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 1.270
_oxdiff_exptl_absorpt_empirical_full_min 0.823