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_7250824
_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 Br N'
_chemical_formula_sum            'C24 H20 Br N'
_chemical_formula_weight         402.336
_chemical_name_systematic
rac-(1R,2R,3R,4S)-3-bromo-1-methyl-2,4-diphenyl-1,2,3,4-tetrahydronaphthalene-1-carbonitrile
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_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                77.854(2)
_cell_angle_beta                 81.908(2)
_cell_angle_gamma                80.281(2)
_cell_formula_units_Z            4
_cell_length_a                   8.9769(2)
_cell_length_b                   12.0076(3)
_cell_length_c                   18.6847(5)
_cell_measurement_reflns_used    15701
_cell_measurement_temperature    293.0(2)
_cell_measurement_theta_max      28.8280
_cell_measurement_theta_min      3.0810
_cell_volume                     1929.09(8)
_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, 2015a)'
_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 0.9987
_diffrn_measured_fraction_theta_max 0.9884
_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    -29.00  88.00   0.25   20.00    --   -0.50  57.00 -90.00  468
  2  \w    -31.00  88.00   0.25   20.00    --   -0.50  38.00 150.00  476
  3  \w    -29.00  88.00   0.25   20.00    --   -0.50  57.00 -30.00  468
  4  \w    -29.00  88.00   0.25   20.00    --   -0.50  57.00 -60.00  468
  5  \w    -31.00  88.00   0.25   20.00    --   -0.50  38.00-150.00  476
  6  \w    -31.00  63.00   0.25   20.00    --   -0.50  38.00  60.00  376
;
_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      -0.0210078000
_diffrn_orient_matrix_UB_12      0.0600216000
_diffrn_orient_matrix_UB_13      -0.0014379000
_diffrn_orient_matrix_UB_21      -0.0416450000
_diffrn_orient_matrix_UB_22      -0.0111200000
_diffrn_orient_matrix_UB_23      0.0353049000
_diffrn_orient_matrix_UB_31      0.0657893000
_diffrn_orient_matrix_UB_32      0.0013629000
_diffrn_orient_matrix_UB_33      0.0166591000
_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  0.0404
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 0.9987
_diffrn_reflns_Laue_measured_fraction_max 0.9884
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            48588
_diffrn_reflns_point_group_measured_fraction_full 0.9987
_diffrn_reflns_point_group_measured_fraction_max 0.9884
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         27.10
_diffrn_reflns_theta_min         2.46
_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    2.137
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.544
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
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    1.385
_exptl_crystal_description       tab
_exptl_crystal_F_000             824.0
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane'
_exptl_crystal_size_max          0.216
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.2750
_refine_diff_density_min         -0.2628
_refine_diff_density_rms         0.0595
_refine_ls_d_res_high            0.7800
_refine_ls_d_res_low             8.2781
_refine_ls_goodness_of_fit_ref   1.0657
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     879
_refine_ls_number_reflns         8412
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0657
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0228
_refine_ls_shift/su_max          -0.0005
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0107P)^2^+0.0682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0357
_refine_ls_wR_factor_ref         0.0381
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -11
_reflns_limit_k_max              15
_reflns_limit_k_min              -14
_reflns_limit_l_max              23
_reflns_limit_l_min              0
_reflns_number_gt                6662
_reflns_number_total             8412
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ra04516a3.cif
_cod_data_source_block           50dia2
_cod_original_cell_volume        1929.10(9)
_cod_database_code               7250824
_chemical_oxdiff_formula         C24H20BrN
_chemical_oxdiff_usercomment     'Dia2 Br'
_olex2_refinement_description
;
;
_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:         PBE
   BASIS SET:      def2-TZVP
   CHARGE:         0
   MULTIPLICITY:   1
   SOLVATION:      CH2CL2
   DATE:           2025-01-21_17-59-03
;
_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 1.711
_oxdiff_exptl_absorpt_empirical_full_min 0.713