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_7250825
_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-(1S,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
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-22 deposited with the CCDC.	2025-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                86.402(3)
_cell_angle_beta                 75.842(3)
_cell_angle_gamma                76.186(3)
_cell_formula_units_Z            4
_cell_length_a                   11.3261(4)
_cell_length_b                   11.5715(5)
_cell_length_c                   16.2185(7)
_cell_measurement_reflns_used    10554
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.5020
_cell_measurement_theta_min      3.1330
_cell_volume                     2001.40(15)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (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  'olex2.refine 1.5 (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 0.9986
_diffrn_measured_fraction_theta_max 0.9987
_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  89.20   0.30   25.00    --    0.80  57.00   0.00  394
  2  \w    -31.00  89.00   0.30   25.00    --    0.80  38.00 -60.00  400
  3  \w    -29.00  89.20   0.30   25.00    --    0.80  57.00  90.00  394
  4  \w    -35.00  89.20   0.30   25.00    --    0.80  29.00-138.14  414
  5  \w    -31.00  87.20   0.30   25.00    --   -1.40  57.00 -90.00  394
  6  \w    -33.00  -8.70   0.30   25.00    --   -1.40  38.00 -30.00   81
;
_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      -0.0025438000
_diffrn_orient_matrix_UB_12      -0.0095468000
_diffrn_orient_matrix_UB_13      0.0439737000
_diffrn_orient_matrix_UB_21      0.0414878000
_diffrn_orient_matrix_UB_22      -0.0566041000
_diffrn_orient_matrix_UB_23      -0.0091469000
_diffrn_orient_matrix_UB_31      0.0517656000
_diffrn_orient_matrix_UB_32      0.0262125000
_diffrn_orient_matrix_UB_33      -0.0042256000
_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  0.0416
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 0.9986
_diffrn_reflns_Laue_measured_fraction_max 0.9987
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            52269
_diffrn_reflns_point_group_measured_fraction_full 0.9986
_diffrn_reflns_point_group_measured_fraction_max 0.9987
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         2.31
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.060
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.672
_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    1.335
_exptl_crystal_description       platelet
_exptl_crystal_F_000             824.0
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.3033
_refine_diff_density_min         -0.2713
_refine_diff_density_rms         0.0568
_refine_ls_d_res_high            0.8000
_refine_ls_d_res_low             8.8276
_refine_ls_goodness_of_fit_ref   1.0248
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    102
_refine_ls_number_parameters     631
_refine_ls_number_reflns         8191
_refine_ls_number_restraints     238
_refine_ls_restrained_S_all      1.0090
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0271
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0303P)^2^+0.3105P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0612
_refine_ls_wR_factor_ref         0.0663
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              14
_reflns_limit_h_min              -13
_reflns_limit_k_max              14
_reflns_limit_k_min              -14
_reflns_limit_l_max              20
_reflns_limit_l_min              0
_reflns_number_gt                6381
_reflns_number_total             8191
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ra04516a3.cif
_cod_data_source_block           LM4-848-F1_50Dia1
_cod_original_cell_volume        2001.41(14)
_cod_database_code               7250825
_chemical_oxdiff_formula         C24H20BrN
_chemical_oxdiff_usercomment     'Dia1 Br'
_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. Restrained distances
 C5_1-C6_1 \\sim C5_1-C6B_1
 C5_2-C6_2 \\sim C5_2-C6B_2
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C5_1, C6_1, C7_1, C8_1, C9_1, C10_1, C11_1, C6B_1, C7B_1, C8B_1, C9B_1,
 C10B_1, C11B_1
 C5_2, C6_2, C7_2, C8_2, C9_2, C10_2, C11_2, C6B_2, C7B_2, C8B_2, C9B_2,
 C10B_2, C11B_2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C6_2, C7_2, C8_2, C9_2, C10_2, C11_2} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C6B_2, C7B_2, C8B_2, C9B_2, C10B_2, C11B_2}
{C6_1, C7_1, C8_1, C9_1, C10_1, C11_1} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C6B_1, C7B_1, C8B_1, C9B_1, C10B_1, C11B_1}
5. Others
 Sof(H5b)=Sof(C6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=Sof(C9B)=Sof(H9B)=
 Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=1-FVAR(1)
 Sof(H5a)=Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=
 Sof(H10)=Sof(C11)=Sof(H11)=FVAR(1)
 Sof(H5b)=Sof(C6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=Sof(C9B)=Sof(H9B)=
 Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=1-FVAR(2)
 Sof(H5a)=Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=
 Sof(H10)=Sof(C11)=Sof(H11)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4), C5(H5a), C5(H5b), C3(H3), C4(H4), C5(H5a), C5(H5b)
6.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C7B(H7B), C8B(H8B), C9B(H9B),
 C10B(H10B), C11B(H11B), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
 C20(H20), C21(H21), C22(H22), C23(H23), C13(H13), C14(H14), C15(H15), C16(H16),
  C17(H17), C20(H20), C21(H21), C22(H22), C23(H23), C7(H7), C8(H8), C9(H9),
 C10(H10), C11(H11), C7B(H7B), C8B(H8B), C9B(H9B), C10B(H10B), C11B(H11B)
6.c Idealised Me refined as rotating group:
 C24(H24a,H24b,H24c), C24(H24a,H24b,H24c)
;
_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 1.359
_oxdiff_exptl_absorpt_empirical_full_min 0.737