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_1573760
_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         'C24 H25 I N2 O'
_chemical_formula_sum            'C24 H25 I N2 O'
_chemical_formula_weight         484.36
_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             2024-01-25
_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                70.882(4)
_cell_angle_beta                 79.329(3)
_cell_angle_gamma                82.137(3)
_cell_formula_units_Z            2
_cell_length_a                   8.6576(3)
_cell_length_b                   11.4823(4)
_cell_length_c                   11.8769(5)
_cell_measurement_reflns_used    7033
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      72.1360
_cell_measurement_theta_min      4.0210
_cell_volume                     1092.57(8)
_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 0.994
_diffrn_measured_fraction_theta_max 0.911
_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   -109.00 -83.00   0.50    1.01    --  -92.45 125.00 -60.00   52
  2  \w   -111.00 -35.00   0.50    1.01    --  -92.45 125.00-120.00  152
  3  \w    -49.00 -19.00   0.50    1.01    --  -92.45 125.00 -60.00   60
  4  \w   -112.00 -62.00   0.50    1.01    --  -92.45 125.00 120.00  100
  5  \w    -99.00 -46.00   0.50    1.01    --  -92.45  77.00 120.00  106
  6  \w    -51.00 -14.00   0.50    1.01    --  -92.45  45.00 150.00   74
  7  \w    -45.00 -12.00   0.50    1.01    --  -92.45  45.00  60.00   66
  8  \w     -8.00  18.00   0.50    1.01    --  -46.98  12.00  96.00   52
  9  \w    -70.00 -17.00   0.50    1.01    --  -92.45  61.00-120.00  106
 10  \w    -44.00 -12.00   0.50    1.01    --  -92.45  45.00-180.00   64
 11  \w    -40.00 -11.00   0.50    1.01    --  -92.45  45.00-150.00   58
 12  \w      4.00  32.00   0.50    1.01    --  -46.98  19.00-120.00   56
 13  \w   -112.00 -19.00   0.50    1.01    --  -46.98 -12.00 -75.00  186
 14  \w   -172.00 -23.00   0.50    1.01    --  -92.45 -12.00 -75.00  298
 15  \w    -20.00  77.00   0.50    1.01    --   45.85 -77.00-180.00  194
 16  \w     61.00  93.00   0.50    1.01    --   97.10 -77.00 -60.00   64
 17  \w     31.00  56.00   0.50    1.01    --   97.10 -77.00 -60.00   50
 18  \w     41.00  70.00   0.50    1.01    --  108.07 -61.00 -60.00   58
 19  \w     74.00 102.00   0.50    1.01    --  108.07 -77.00-180.00   56
 20  \w     32.00  62.00   0.50    1.01    --  108.07 -61.00-150.00   60
 21  \w     17.00  43.00   0.50    1.01    --   97.10 -45.00-180.00   52
 22  \w     21.00  47.00   0.50    1.01    --   97.10 -45.00-150.00   52
 23  \w     17.00  50.00   0.50    1.01    --   97.10 -45.00-120.00   66
 24  \w     36.00  62.00   0.50    1.01    --  108.07 -61.00  60.00   52
 25  \w     18.00  47.00   0.50    1.01    --   97.10 -45.00 150.00   58
 26  \w     64.00 111.00   0.50    1.01    --   97.10  12.00  96.00   94
 27  \w     72.00 163.00   0.50    1.01    --  108.07  12.00  96.00  182
 28  \w     35.00  60.00   0.50    1.01    --   97.10  12.00  96.00   50
 29  \w     39.00 118.00   0.50    1.01    --   45.85  12.00  96.00  158
 30  \w    153.00 178.00   0.50    1.01    --  108.07  45.00 -90.00   50
 31  \w     35.00  82.00   0.50    1.01    --  108.07 -95.00  30.00   94
 32  \w     39.00  64.00   0.50    1.01    --  108.07-125.00 120.00   50
 33  \w     46.00  77.00   0.50    1.01    --   97.10 -95.00 150.00   62
 34  \w     87.00 112.00   0.50    1.01    --  108.07-125.00 120.00   50
;
_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      0.1460133000
_diffrn_orient_matrix_UB_12      -0.0875245000
_diffrn_orient_matrix_UB_13      -0.0213975000
_diffrn_orient_matrix_UB_21      0.1081135000
_diffrn_orient_matrix_UB_22      0.0978995000
_diffrn_orient_matrix_UB_23      -0.0044346000
_diffrn_orient_matrix_UB_31      -0.0013087000
_diffrn_orient_matrix_UB_32      -0.0552792000
_diffrn_orient_matrix_UB_33      0.1371224000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.911
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            10702
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.911
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.236
_diffrn_reflns_theta_min         3.984
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.628
_exptl_absorpt_correction_T_max  0.858
_exptl_absorpt_correction_T_min  0.516
_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    1.472
_exptl_crystal_description       plate
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.719
_refine_diff_density_min         -0.968
_refine_diff_density_rms         0.085
_refine_ls_extinction_coef       0.00068(18)
_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   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     270
_refine_ls_number_reflns         4218
_refine_ls_number_restraints     234
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0373
_refine_ls_R_factor_gt           0.0325
_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^)+(0.0421P)^2^+0.9435P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0817
_refine_ls_wR_factor_ref         0.0853
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3809
_reflns_number_total             4218
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05760k2.cif
_cod_data_source_block           rja240002_fa
_cod_depositor_comments
'Adding full bibliography for 1573760--1573765.cif.'
_cod_database_code               1573760
_chemical_oxdiff_formula         'C24 H25 I1 N2 O1'
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.389
_diffrn_oxdiff_digest_frames
;
0197dd7e5a3021e6522763bfd0bf5e6c48029825b5c
;
_diffrn_oxdiff_digest_hkl
;
01b657ec46f6d091fb4e48520943f83fd9bf83
;
_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
 I1A-C18 \\sim I1B-C22
 with sigma of 0.02
 C24B-C18 \\sim C24A-C22
 with sigma of 0.02
 C24B-C19 \\sim C24B-C17
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
I1B \\sim C24A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(I1A) = Uanis(C24B)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: I1A(0.9015) C24A(0.9015) H24A(0.9015) H24B(0.9015) H24C(0.9015)
 I1B(0.0985) C24B(0.0985) H24F(0.0985) H24D(0.0985) H24E(0.0985)
6.a Ternary CH refined with riding coordinates:
 C4(H4)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C19(H19), C21(H21)
6.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C23(H23A,H23B,H23C), C24A(H24A,H24B,H24C), C24B(H24F,H24D,
 H24E)
;
_shelx_res_checksum              73476
_shelx_hkl_checksum              62806
_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 1.549
_oxdiff_exptl_absorpt_empirical_full_min 0.804