Cu/Pd dual catalyzed stereoselective construction of vicinal tri- and tetrasubstituted stereocenters connected to chiral α-arylacetonitriles
Mimoun, Liliane; Sanaa, Hamdi; Heppner, Florian; Gérard, Hélène; Réset, Laurine; West, Caroline; Vanthuyne, Nicolas; Retailleau, Pascal; Nicolas, Cyril; Gillaizeau, Isabelle; RSC Advances 15 (2025) 30915–30920; doi:10.1039/D5RA04516A

data_7250823
_publ_section_title
;
 Cu/Pd dual catalyzed stereoselective construction of vicinal tri- and
 tetrasubstituted stereocenters connected to chiral \a-arylacetonitriles
;
_journal_issue                   37
_journal_name_full               'RSC Advances'
_journal_page_first              30915
_journal_page_last               30920
_journal_paper_doi               10.1039/D5RA04516A
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C24 H20 N2 O2'
_chemical_formula_sum            'C24 H20 N2 O2'
_chemical_formula_weight         368.439
_chemical_name_systematic
;
'2R,3R,E)-2-methyl-2-(4-nitrophenyl)-3,5-diphenylpent-4-enenitrile'
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_Int_Tables_number      14
_audit_creation_date             2024-11-13
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2024-11-13 deposited with the CCDC.	2025-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.047(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4802(5)
_cell_length_b                   11.7086(6)
_cell_length_c                   17.1437(10)
_cell_measurement_reflns_used    8954
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.5470
_cell_measurement_theta_min      2.3960
_cell_volume                     1900.26(18)
_computing_cell_refinement       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.141a 64-bit (release 04-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement
'olex2.refine 1.5-ac6-020 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.9994
_diffrn_measured_fraction_theta_max 0.9992
_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      5.00  91.00   0.50   10.00    --    8.20  57.00  60.00  172
  2  \w    -14.00  67.00   0.50   10.00    --    8.20  60.00-165.57  162
  3  \w    -15.00  88.00   0.50   10.00    --    8.20  57.00 -30.00  206
  4  \w     30.00  97.00   0.50   10.00    --    8.20  57.00 -90.00  134
  5  \w    -52.00 -26.00   0.50   10.00    --   -9.30  57.00  30.00   52
  6  \w    -14.00  79.00   0.50   10.00    --   -9.30  57.00  30.00  186
  7  \w    -30.00  52.00   0.50   10.00    --   -9.30  57.00 150.00  164
  8  \w      7.00  35.00   0.50   10.00    --    8.20  60.00 104.43   56
  9  \w      5.00  31.00   0.50   10.00    --    8.20  59.00 -98.79   52
 10  \w     31.00  57.00   0.50   10.00    --   -9.30  38.00  60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0091674000
_diffrn_orient_matrix_UB_12      0.0578096000
_diffrn_orient_matrix_UB_13      -0.0109898000
_diffrn_orient_matrix_UB_21      -0.0488003000
_diffrn_orient_matrix_UB_22      -0.0078640000
_diffrn_orient_matrix_UB_23      -0.0323923000
_diffrn_orient_matrix_UB_31      -0.0561152000
_diffrn_orient_matrix_UB_32      0.0163188000
_diffrn_orient_matrix_UB_33      0.0233762000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0345
_diffrn_reflns_Laue_measured_fraction_full 0.9994
_diffrn_reflns_Laue_measured_fraction_max 0.9992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            29638
_diffrn_reflns_point_group_measured_fraction_full 0.9994
_diffrn_reflns_point_group_measured_fraction_max 0.9992
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         2.11
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.340
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.141a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.288
_exptl_crystal_description       prism
_exptl_crystal_F_000             776
_exptl_crystal_size_max          0.429
_exptl_crystal_size_mid          0.303
_exptl_crystal_size_min          0.182
_refine_diff_density_max         0.3641
_refine_diff_density_min         -0.2481
_refine_diff_density_rms         0.0443
_refine_ls_d_res_high            0.8000
_refine_ls_d_res_low             9.6644
_refine_ls_goodness_of_fit_ref   1.0527
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     433
_refine_ls_number_reflns         3870
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.0517
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0414
_refine_ls_shift/su_max          -0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0563P)^2^+0.2084P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1023
_refine_ls_wR_factor_ref         0.1114
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -11
_reflns_limit_k_max              14
_reflns_limit_k_min              0
_reflns_limit_l_max              21
_reflns_limit_l_min              -9
_reflns_number_gt                2968
_reflns_number_total             3870
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ra04516a3.cif
_cod_data_source_block           HS608-P
_cod_original_cell_volume        1900.25(18)
_cod_database_code               7250823
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(H6) \\sim Ueq: with sigma of 0.03 and sigma for terminal atoms of 0.06
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         R2SCAN
   BASIS SET:      cc-pVTZ
   CHARGE:         0
   MULTIPLICITY:   1
   SOLVATION:      CH2CL2
   DATE:           2024-11-13_10-51-24
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.583
_oxdiff_exptl_absorpt_empirical_full_min 0.556