Stereoselective synthesis of atropisomeric amides enabled by intramolecular acyl transfer.
Wootton, Jack M.; Roper, Natalie J.; Morris, Catrin E.; Maguire, Victoria E.; Duff, Lee C.; Waddell, Paul G.; Whitwood, Adrian C.; Gammons, Richard J.; Miah, Afjal H.; Lynam, Jason M.; Armstrong, Roly J.; Unsworth, William P.; Chemical science 16 (2025) 3938–3945; doi:10.1039/d4sc05760k

data_1573764
_publ_section_title
;
 Stereoselective synthesis of atropisomeric amides enabled by
 intramolecular acyl transfer.
;
_journal_issue                   9
_journal_name_full               'Chemical science'
_journal_page_first              3938
_journal_page_last               3945
_journal_paper_doi               10.1039/d4sc05760k
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C25 H28 N2 O'
_chemical_formula_sum            'C25 H28 N2 O'
_chemical_formula_weight         372.49
_chemical_melting_point          407.5(15)
_chemical_name_systematic
N-(2-(tert-butyl)phenyl)-N-(phenyl(pyridin-2-yl)methyl)propionamide
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-17 deposited with the CCDC.	2025-01-23 downloaded from the CCDC.
;
_cell_angle_alpha                100.7280(10)
_cell_angle_beta                 100.9090(10)
_cell_angle_gamma                105.8830(10)
_cell_formula_units_Z            4
_cell_length_a                   9.02470(10)
_cell_length_b                   13.2322(2)
_cell_length_c                   18.6064(3)
_cell_measurement_reflns_used    14274
_cell_measurement_temperature    109.95(10)
_cell_measurement_theta_max      76.6200
_cell_measurement_theta_min      3.5880
_cell_volume                     2030.78(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.112a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.112a 64-bit (release 01-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.112a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      109.95(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -46.00 -14.00   0.50    0.30    --  -48.64  82.00   3.00   64
  2  \w    -19.00  73.00   0.50    0.30    --   48.64 -82.00-118.00  184
  3  \w     63.00  88.00   0.50    1.20    --  107.75 -82.00-118.00   50
  4  \w    105.00 136.00   0.50    1.20    --  107.75  82.00   3.00   62
  5  \w   -118.00 -84.00   0.50    0.30    --  -48.64-125.00 -90.00   68
  6  \w   -116.00 -73.00   0.50    0.30    --  -48.64-125.00   0.00   86
  7  \w   -118.00 -84.00   0.50    0.30    --  -48.64-125.00  30.00   68
  8  \w   -117.00 -74.00   0.50    0.30    --  -48.64-125.00 -60.00   86
  9  \w    -16.00  11.00   0.50    0.30    --   48.64 -37.00 -30.00   54
 10  \w     41.00  93.00   0.50    0.30    --   48.64-125.00-150.00  104
 11  \w    -16.00  59.00   0.50    0.30    --   48.64 -37.00 -90.00  150
 12  \w    -22.00  32.00   0.50    0.30    --   48.64 -37.00-180.00  108
 13  \w     95.00 178.00   0.50    1.20    --  107.75  15.00  30.00  166
 14  \w     41.00  79.00   0.50    1.20    --  107.75-125.00 150.00   76
 15  \w     37.00 106.00   0.50    1.20    --  107.75 -94.00-180.00  138
 16  \w     87.00 112.00   0.50    1.20    --  107.75-125.00 150.00   50
 17  \w     39.00  69.00   0.50    1.20    --  107.75-125.00  90.00   60
 18  \w     35.00 105.00   0.50    1.20    --  107.75 -94.00-150.00  140
 19  \w     79.00 130.00   0.50    1.20    --  107.75 -77.00 -60.00  102
 20  \w    118.00 178.00   0.50    1.20    --  107.75 125.00 -90.00  120
 21  \w     37.00 120.00   0.50    1.20    --  107.75 -61.00 -90.00  166
 22  \w     33.00  80.00   0.50    1.20    --  107.75 -30.00-180.00   94
 23  \w     60.00 105.00   0.50    1.20    --  107.75 -94.00  60.00   90
 24  \w     95.00 172.00   0.50    1.20    --  107.75  30.00 -90.00  154
 25  \w     94.00 176.00   0.50    1.20    --  107.75  15.00   0.00  164
 26  \w     87.00 112.00   0.50    1.20    --  107.75-125.00  90.00   50
 27  \w     65.00  91.00   0.50    1.20    --  107.75 -94.00-120.00   52
 28  \w     96.00 174.00   0.50    1.20    --  107.75  30.00 -60.00  156
 29  \w     51.00 106.00   0.50    1.20    --  107.75 -94.00 -60.00  110
 30  \w     38.00  64.00   0.50    1.20    --  107.75 -94.00  90.00   52
 31  \w     38.00  81.00   0.50    1.20    --  107.75 -45.00  30.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1264759000
_diffrn_orient_matrix_UB_12      -0.0473938000
_diffrn_orient_matrix_UB_13      0.0404926000
_diffrn_orient_matrix_UB_21      -0.1317614000
_diffrn_orient_matrix_UB_22      0.0053555000
_diffrn_orient_matrix_UB_23      -0.0638547000
_diffrn_orient_matrix_UB_31      -0.0178214000
_diffrn_orient_matrix_UB_32      -0.1156309000
_diffrn_orient_matrix_UB_33      -0.0433000000
_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  0.0224
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            21553
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.237
_diffrn_reflns_theta_min         3.589
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.574
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.599
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.112a (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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_recrystallization_method
'hexane and dichloromethane slow evaporation'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.278
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.036
_refine_ls_extinction_coef       0.00076(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     514
_refine_ls_number_reflns         7416
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0393
_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^)+(0.0497P)^2^+0.5440P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1064
_refine_ls_wR_factor_ref         0.1103
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6447
_reflns_number_total             7416
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05760k2.cif
_cod_data_source_block           wpu24011
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '406-409' was changed to
'407.5(15)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1573760--1573765.cif.
;
_cod_database_code               1573764
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H28 N2 O1'
_chemical_oxdiff_usercomment     'JAck Wooton jmw11-104-P'
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.879
_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:
 C31(H31), C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C39(H39A,H39B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C4(H4), C42(H42), C2(H2), C29(H29), C20(H20), C45(H45), C1(H1),
 C27(H27), C33(H33), C18(H18), C19(H19), C3(H3), C43(H43), C8(H8), C12(H12),
 C26(H26), C44(H44), C37(H37), C35(H35), C28(H28), C9(H9), C11(H11), C36(H36),
 C34(H34), C10(H10)
2.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C15(H15A,H15B,
 H15C), C24(H24A,H24B,H24C), C50(H50A,H50B,H50C), C48(H48A,H48B,H48C), C49(H49A,
 H49B,H49C)
;
_shelx_res_checksum              65048
_shelx_hkl_checksum              61188
_olex2_date_sample_data_collection 2024-03-08
_olex2_date_sample_submission    2024-03-06
_olex2_exptl_crystal_mounting_method 'oil on 200 micrometre micromount'
_olex2_submission_original_sample_id jmw11-104-P
_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 1.404
_oxdiff_exptl_absorpt_empirical_full_min 0.710