A stereodivergent multicomponent approach for the synthesis of C-N atropisomeric peptide analogues.
Roper, Natalie J.; Campbell, Aaron D. G.; Waddell, Paul G.; Brown, Alistair K.; Ermanis, Kristaps; Armstrong, Roly J.; Chemical science 15 (2024) 16743–16751; doi:10.1039/d4sc04700a

data_1573026
_publ_section_title
;
 A stereodivergent multicomponent approach for the synthesis of C-N
 atropisomeric peptide analogues.
;
_journal_issue                   40
_journal_name_full               'Chemical science'
_journal_page_first              16743
_journal_page_last               16751
_journal_paper_doi               10.1039/d4sc04700a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C29 H34 N2 O2'
_chemical_formula_sum            'C29 H34 N2 O2'
_chemical_formula_weight         442.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-01-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.12.01 svn.r5f60950 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-05-15 deposited with the CCDC.	2024-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.9500(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.1161(2)
_cell_length_b                   12.9639(2)
_cell_length_c                   14.5367(2)
_cell_measurement_reflns_used    18194
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      77.8860
_cell_measurement_theta_min      3.9050
_cell_volume                     2581.75(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_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 0.938
_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    -63.00 -23.00   0.50    0.46    --  -92.01  77.00 -60.00   80
  2  \w    -47.00 -21.00   0.50    0.46    --  -92.01  45.00-120.00   52
  3  \w    -51.00 -26.00   0.50    0.46    --  -92.01  45.00 -60.00   50
  4  \w    -49.00 -15.00   0.50    0.46    --  -92.01  45.00-150.00   68
  5  \w    -47.00 -22.00   0.50    0.46    --  -92.01  45.00  60.00   50
  6  \w    -46.00 -20.00   0.50    0.46    --  -92.01  45.00  90.00   52
  7  \w    -71.00 -43.00   0.50    0.46    --  -92.01  61.00 150.00   56
  8  \w    -51.00 -16.00   0.50    0.46    --  -92.01  45.00 150.00   70
  9  \w    -51.00 -19.00   0.50    0.46    --  -92.01  45.00 120.00   64
 10  \w    -27.00  22.00   0.50    0.46    --  -49.76  19.00 -60.00   98
 11  \w    -12.00  28.00   0.50    0.46    --  -49.76  19.00-120.00   80
 12  \w    -26.00  28.00   0.50    0.46    --  -49.76  19.00 120.00  108
 13  \w     80.00 109.00   0.50    0.46    --   48.76 123.00 -67.00   58
 14  \w    102.00 127.00   0.50    0.46    --  108.00 123.00 -67.00   50
 15  \w     86.00 111.00   0.50    0.46    --  108.00 150.00  94.00   50
 16  \w     58.00 118.00   0.50    0.46    --   48.76 150.00  94.00  120
 17  \w     78.00 121.00   0.50    0.46    --   48.76 125.00  90.00   86
 18  \w     76.00 114.00   0.50    0.46    --   96.11  61.00  90.00   76
 19  \w    126.00 155.00   0.50    0.46    --   96.11  61.00  90.00   58
 20  \w     48.00  73.00   0.50    0.46    --  108.00 -95.00-120.00   50
 21  \w     73.00  98.00   0.50    0.46    --  108.00-123.00-148.00   50
 22  \w     36.00  80.00   0.50    0.46    --   48.76-123.00-148.00   88
 23  \w     60.00  85.00   0.50    0.46    --  108.00-150.00  49.00   50
 24  \w     73.00 101.00   0.50    0.46    --  108.00-125.00 150.00   56
 25  \w     37.00  63.00   0.50    0.46    --  108.00-125.00 150.00   52
 26  \w    -30.00  22.00   0.50    0.46    --   48.76 -19.00  90.00  104
 27  \w     18.00  51.00   0.50    0.46    --   96.11 -45.00   0.00   66
 28  \w     43.00  70.00   0.50    0.46    --  108.00 -77.00  30.00   54
 29  \w     24.00  50.00   0.50    0.46    --   96.11 -45.00  90.00   52
 30  \w     20.00  45.00   0.50    0.46    --   96.11 -45.00  30.00   50
 31  \w     37.00  62.00   0.50    0.46    --  108.00 -61.00 -30.00   50
 32  \w     57.00 102.00   0.50    0.46    --  108.00 -77.00 -60.00   90
 33  \w     44.00  69.00   0.50    0.46    --  108.00 -61.00-180.00   50
 34  \w    -27.00  38.00   0.50    0.46    --   48.76 -38.00-180.00  130
 35  \w   -164.00 -40.00   0.50    0.46    --  -92.01 -15.00 -30.00  248
 36  \w   -112.00 -87.00   0.50    0.46    --  -49.76-150.00  49.00   50
 37  \w   -133.00-108.00   0.50    0.46    --  -92.01-150.00  49.00   50
 38  \w   -137.00-112.00   0.50    0.46    --  -92.01-123.00-148.00   50
 39  \w   -107.00 -33.00   0.50    0.46    --  -99.00 105.00 -43.54  148
 40  \w    -65.00 -40.00   0.50    0.46    --  -92.01 123.00 -67.00   50
 41  \w   -107.00 -33.00   0.50    0.46    --  -99.00 108.00-111.72  148
 42  \w    -59.00 -34.00   0.50    0.46    --  -49.76 123.00 -67.00   50
 43  \w   -108.00 -52.00   0.50    0.46    --  -99.00 109.00  49.44  112
 44  \w   -129.00 -52.00   0.50    0.46    --  -92.01 150.00  94.00  154
;
_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      0.1014876000
_diffrn_orient_matrix_UB_12      0.0365167000
_diffrn_orient_matrix_UB_13      -0.0085071000
_diffrn_orient_matrix_UB_21      -0.0362482000
_diffrn_orient_matrix_UB_22      0.1125520000
_diffrn_orient_matrix_UB_23      -0.0082445000
_diffrn_orient_matrix_UB_31      0.0323905000
_diffrn_orient_matrix_UB_32      0.0114192000
_diffrn_orient_matrix_UB_33      0.1084123000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.938
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            30909
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.327
_diffrn_reflns_theta_min         3.918
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.555
_exptl_absorpt_correction_T_max  0.958
_exptl_absorpt_correction_T_min  0.935
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (Rigaku Oxford Diffraction, 2022)
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    1.139
_exptl_crystal_description       prism
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.266
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.00119(17)
_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   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         5208
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0387
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0486P)^2^+0.6746P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1004
_refine_ls_wR_factor_ref         0.1042
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4592
_reflns_number_total             5208
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc04700a3.cif
_cod_data_source_block           rja230005_fa
_cod_database_code               1573026
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C29 H34 N2 O2'
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.902
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C15(H15), C16(H16), C17(H17),
 C18(H18), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              76585
_shelx_hkl_checksum              61726
_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 1.309
_oxdiff_exptl_absorpt_empirical_full_min 0.710