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_7250822
_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_absolute_configuration unk
_chemical_formula_moiety         'C24 H21 N'
_chemical_formula_sum            'C24 H21 N'
_chemical_formula_weight         323.441
_chemical_name_systematic
((2S,3S)or(2R,3R),E)-2-methyl-2,3,5-triphenylpent-4-enenitrile
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_Int_Tables_number      4
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-22
_audit_creation_method
;
Olex2 1.5-ac6-016
(compiled 2024.01.13 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6897)
;
_audit_update_record
;
2025-01-22 deposited with the CCDC.	2025-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.991(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.5532(9)
_cell_length_b                   6.4625(4)
_cell_length_c                   13.2348(10)
_cell_measurement_reflns_used    7162
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.3050
_cell_measurement_theta_min      3.2090
_cell_volume                     939.83(12)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_computing_molecular_graphics    'Olex2 1.5-ac6-016 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-016 (Dolomanov et al., 2009)'
_computing_structure_refinement
'olex2.refine 1.5-ac6-016 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.9973
_diffrn_measured_fraction_theta_max 0.9970
_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    -31.00  90.00   0.50   15.00    --    0.60  38.00 -60.00  242
  2  \w    -29.00  90.00   0.50   15.00    --    0.60  57.00  90.00  238
  3  \w    -29.00  90.00   0.50   15.00    --    0.60  57.00-180.00  238
  4  \w    -29.00  90.00   0.50   15.00    --    0.60  57.00 120.00  238
  5  \w    -31.00  88.00   0.50   15.00    --   -1.30  57.00-150.00  238
  6  \w    -33.00  36.50   0.50   15.00    --   -1.30  38.00  30.00  139
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0021543000
_diffrn_orient_matrix_UB_12      0.0138214000
_diffrn_orient_matrix_UB_13      -0.0524988000
_diffrn_orient_matrix_UB_21      -0.0434913000
_diffrn_orient_matrix_UB_22      -0.0799754000
_diffrn_orient_matrix_UB_23      -0.0178940000
_diffrn_orient_matrix_UB_31      -0.0477359000
_diffrn_orient_matrix_UB_32      0.0739094000
_diffrn_orient_matrix_UB_33      -0.0096328000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 0.9973
_diffrn_reflns_Laue_measured_fraction_max 0.9970
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            23245
_diffrn_reflns_point_group_measured_fraction_full 0.9985
_diffrn_reflns_point_group_measured_fraction_max 0.9861
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         27.48
_diffrn_reflns_theta_min         3.24
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.066
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.751
_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,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.143
_exptl_crystal_description       prism
_exptl_crystal_F_000             344.178
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.0825
_refine_diff_density_min         -0.1034
_refine_diff_density_rms         0.0227
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   -1.5(16)
_refine_ls_d_res_high            0.7701
_refine_ls_d_res_low             6.2938
_refine_ls_goodness_of_fit_ref   1.1136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     415
_refine_ls_number_reflns         4249
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.1136
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0244
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0060P)^2^+0.0118P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0430
_refine_ls_wR_factor_ref         0.0459
_reflns_Friedel_coverage         0.973
_reflns_limit_h_max              14
_reflns_limit_h_min              -15
_reflns_limit_k_max              8
_reflns_limit_k_min              -8
_reflns_limit_l_max              17
_reflns_limit_l_min              -17
_reflns_number_gt                3427
_reflns_number_total             4249
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ra04516a3.cif
_cod_data_source_block           exp_888
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               7250822
_chemical_oxdiff_formula         C24H21N
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
;
_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:           2025-01-22_09-57-25
;
_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 1.542
_oxdiff_exptl_absorpt_empirical_full_min 0.628