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_1573765
_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         'C30 H30 N2 O'
_chemical_formula_sum            'C30 H30 N2 O'
_chemical_formula_weight         434.56
_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             2024-04-11
_audit_creation_method
;
Olex2 1.5-ac5-023
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-06-13 deposited with the CCDC.	2025-01-23 downloaded from the CCDC.
;
_cell_angle_alpha                95.7950(10)
_cell_angle_beta                 99.0840(10)
_cell_angle_gamma                96.9800(10)
_cell_formula_units_Z            2
_cell_length_a                   9.02320(10)
_cell_length_b                   10.84450(10)
_cell_length_c                   12.5529(2)
_cell_measurement_reflns_used    24899
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      77.1670
_cell_measurement_theta_min      3.6350
_cell_volume                     1194.85(3)
_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-ac5-023 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.947
_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     74.00 122.00   0.50    0.34    --   46.35 125.00 -60.00   96
  2  \w     -6.00  23.00   0.50    0.34    --   38.00  99.00  52.36   58
  3  \w    -47.00 -11.00   0.50    0.34    --   10.00 123.00 -20.11   72
  4  \w     15.00  43.00   0.50    0.34    --   50.00  84.00 160.62   56
  5  \w    -44.00 -13.00   0.50    0.34    --   14.00 125.00-142.20   62
  6  \w     16.00  43.00   0.50    0.34    --   50.00  83.00-153.48   54
  7  \w     13.00  43.00   0.50    0.34    --   50.00  87.00-126.49   60
  8  \w     17.00  43.00   0.50    0.34    --   54.00  87.00 -57.49   52
  9  \w     15.00  43.00   0.50    0.34    --   54.00  90.00-129.64   56
 10  \w     15.00  42.00   0.50    0.34    --   54.00  91.00 -13.58   54
 11  \w     16.00  43.00   0.50    0.34    --   54.00  89.00  75.53   54
 12  \w     17.00  43.00   0.50    0.34    --   54.00  88.00 123.91   52
 13  \w     85.00 172.00   0.50    0.34    --   97.10 102.00 118.00  174
 14  \w     85.00 178.00   0.50    0.34    --  108.07 102.00 118.00  186
 15  \w     39.00 141.00   0.50    0.34    --   70.00  77.00 144.92  204
 16  \w     66.00 168.00   0.50    0.34    --   97.10  77.00  60.00  204
 17  \w     77.00 178.00   0.50    0.34    --  108.07  77.00   0.00  202
 18  \w     32.00 133.00   0.50    0.34    --   62.00  76.00  38.59  202
 19  \w     39.00 141.00   0.50    0.34    --   70.00  77.00 -62.46  204
 20  \w     40.00 141.00   0.50    0.34    --   70.00  76.00-117.03  202
 21  \w     66.00 168.00   0.50    0.34    --   97.10  77.00-180.00  204
 22  \w     32.00 133.00   0.50    0.34    --   62.00  76.00-154.11  202
 23  \w     36.00 138.00   0.50    0.34    --   66.00  75.00  -0.39  204
 24  \w     32.00 134.00   0.50    0.34    --   62.00  75.00  65.81  204
 25  \w     23.00 125.00   0.50    0.34    --   46.35  57.00  90.00  204
 26  \w     83.00 178.00   0.50    0.34    --  108.07  61.00 120.00  190
 27  \w     23.00 125.00   0.50    0.34    --   46.35  57.00 -30.00  204
 28  \w     16.00  51.00   0.50    0.34    --   97.10 -45.00-120.00   70
 29  \w     27.00 105.00   0.50    0.34    --   97.10 -77.00  30.00  156
 30  \w     31.00  71.00   0.50    0.34    --  108.07 -61.00  90.00   80
 31  \w     16.00  51.00   0.50    0.34    --   97.10 -45.00  60.00   70
 32  \w     33.00 112.00   0.50    0.34    --  108.07-125.00   0.00  158
 33  \w     22.00 107.00   0.50    0.34    --   97.10-102.00  15.00  170
 34  \w     33.00 107.00   0.50    0.34    --  108.07-102.00  15.00  148
 35  \w     35.00 105.00   0.50    0.34    --  108.07 -95.00-150.00  140
 36  \w    -14.00  92.00   0.50    0.34    --   46.35-102.00  15.00  212
 37  \w   -149.00 -47.00   0.50    0.34    --  -78.00 -77.00 153.45  204
 38  \w   -149.00 -47.00   0.50    0.34    --  -78.00 -76.00 173.74  204
 39  \w   -163.00 -61.00   0.50    0.34    --  -92.45 -77.00 -60.00  204
 40  \w   -161.00 -59.00   0.50    0.34    --  -90.00 -77.00 -87.02  204
 41  \w   -163.00 -61.00   0.50    0.34    --  -92.45 -77.00-120.00  204
 42  \w   -170.00 -69.00   0.50    0.34    --  -99.00 -75.00-127.07  202
 43  \w   -163.00 -61.00   0.50    0.34    --  -92.45 -77.00-150.00  204
 44  \w   -137.00 -36.00   0.50    0.34    --  -66.00 -75.00-129.19  202
 45  \w   -153.00 -51.00   0.50    0.34    --  -82.00 -76.00   2.74  204
 46  \w   -171.00 -69.00   0.50    0.34    --  -99.00 -74.00 -31.06  204
 47  \w   -158.00 -56.00   0.50    0.34    --  -86.00 -74.00 -33.12  204
 48  \w   -142.00 -69.00   0.50    0.34    --  -70.00 -74.00-146.34  146
 49  \w   -137.00 -35.00   0.50    0.34    --  -66.00 -76.00  71.95  204
 50  \w   -154.00 -52.00   0.50    0.34    --  -82.00 -74.00  62.96  204
 51  \w   -154.00 -52.00   0.50    0.34    --  -82.00 -74.00 101.69  204
 52  \w   -158.00 -56.00   0.50    0.34    --  -86.00 -74.00 143.38  204
 53  \w   -144.00 -43.00   0.50    0.34    --  -70.00 -69.00  62.26  202
 54  \w   -144.00 -43.00   0.50    0.34    --  -70.00 -68.00  36.17  202
 55  \w   -159.00 -57.00   0.50    0.34    --  -86.00 -72.00 -23.96  204
 56  \w   -163.00 -61.00   0.50    0.34    --  -90.00 -72.00  32.63  204
 57  \w   -174.00 -72.00   0.50    0.34    --  -99.00 -67.00  67.04  204
 58  \w   -169.00 -68.00   0.50    0.34    --  -94.00 -66.00  89.17  202
 59  \w   -168.00 -85.00   0.50    0.34    --  -92.45-102.00  15.00  166
 60  \w   -105.00 -22.00   0.50    0.34    --  -92.45  77.00 -60.00  166
 61  \w   -112.00 -16.00   0.50    0.34    --  -92.45 125.00 120.00  192
 62  \w   -106.00 -17.00   0.50    0.34    --  -92.45 102.00 118.00  178
 63  \w    -93.00  14.00   0.50    0.34    --  -47.35 102.00 118.00  214
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0668972000
_diffrn_orient_matrix_UB_12      0.1108665000
_diffrn_orient_matrix_UB_13      -0.0475279000
_diffrn_orient_matrix_UB_21      -0.0549008000
_diffrn_orient_matrix_UB_22      -0.0818381000
_diffrn_orient_matrix_UB_23      -0.1101285000
_diffrn_orient_matrix_UB_31      -0.1516663000
_diffrn_orient_matrix_UB_32      -0.0425087000
_diffrn_orient_matrix_UB_33      0.0359859000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            43526
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.302
_diffrn_reflns_theta_min         3.593
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.564
_exptl_absorpt_correction_T_max  0.981
_exptl_absorpt_correction_T_min  0.929
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.208
_exptl_crystal_description       block
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.251
_refine_diff_density_min         -0.179
_refine_diff_density_rms         0.034
_refine_ls_extinction_coef       0.0039(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/1 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         4796
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0398
_refine_ls_R_factor_gt           0.0360
_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^)+(0.0464P)^2^+0.3235P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0940
_refine_ls_wR_factor_ref         0.0969
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4305
_reflns_number_total             4796
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05760k2.cif
_cod_data_source_block           rja240003_fa
_cod_depositor_comments
'Adding full bibliography for 1573760--1573765.cif.'
_cod_database_code               1573765
_chemical_oxdiff_formula         'C30 H30 N2 O1'
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.905
_diffrn_oxdiff_digest_frames
;
01441f30b879a3b0ffa1fdcc926f19d069102561f01
;
_diffrn_oxdiff_digest_hkl
;
014e838c22036cfff106ccddc2b0770e4c335d
;
_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:
 C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C21(H21),
 C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30)
2.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              54878
_shelx_hkl_checksum              49428
_shelx_shelxl_version_number     2019/1
_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 1.280
_oxdiff_exptl_absorpt_empirical_full_min 0.717