Decoded fingerprints of hyperresponsive, expanding product space: polyether cascade cyclizations as tools to elucidate supramolecular catalysis
Chen, Hao; Li, Tian-Ren; Sakai, Naomi; Besnard, Celine; Guénée, Laure; Pupier, Marion; Viger-Gravel, Jasmine; Tiefenbacher, Konrad; Matile, Stefan; Chemical Science 13 (2022) 10273–10280; doi:10.1039/D2SC03991E

data_1567646
_publ_section_title
;
 Decoded fingerprints of hyperresponsive, expanding product space:
 polyether cascade cyclizations as tools to elucidate supramolecular
 catalysis
;
_journal_issue                   35
_journal_name_full               'Chemical Science'
_journal_page_first              10273
_journal_page_last               10280
_journal_paper_doi               10.1039/D2SC03991E
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C35 H38 O4'
_chemical_formula_sum            'C35 H38 O4'
_chemical_formula_weight         522.65
_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             2022-05-31
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-06-02 deposited with the CCDC.	2022-08-18 downloaded from the CCDC.
;
_cell_angle_alpha                89.562(2)
_cell_angle_beta                 87.114(2)
_cell_angle_gamma                78.209(3)
_cell_formula_units_Z            2
_cell_length_a                   6.28197(17)
_cell_length_b                   12.2599(4)
_cell_length_c                   19.1503(5)
_cell_measurement_reflns_used    16059
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      73.2430
_cell_measurement_theta_min      2.2980
_cell_volume                     1441.93(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.959
_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    -56.00 -25.00   0.50    7.00    --  -59.37 -15.00  60.00   62
  2  \w    -96.00 -53.00   0.50    7.00    --  -59.37   0.00-180.00   86
  3  \w   -106.00 -64.00   0.50    7.00    --  -59.37 -15.00  60.00   84
  4  \w    -71.00 -18.00   0.50    7.00    --  -59.37   0.00-150.00  106
  5  \w    -99.00 -35.00   0.50    7.00    --  -59.37   0.00 -60.00  128
  6  \w    -79.00 -53.00   0.50    7.00    --  -59.37 125.00 120.00   52
  7  \w     18.00  66.00   0.50    7.00    --   59.80 -94.00-120.00   96
  8  \w     18.00  54.00   0.50    7.00    --   59.80 -94.00   0.00   72
  9  \w     19.00  71.00   0.50    7.00    --   59.80 -94.00 120.00  104
 10  \w     19.00  72.00   0.50    7.00    --   59.80 -94.00 -60.00  106
 11  \w     19.00  50.00   0.50    7.00    --   59.80 -94.00  60.00   62
 12  \w     59.00  85.00   0.50    7.00    --   73.77 -94.00  30.00   52
 13  \w     40.00  66.00   0.50    7.00    --   76.98 -94.00-120.00   52
 14  \w     43.00  84.00   0.50    7.00    --   76.98  15.00  30.00   82
 15  \w     36.00  85.00   0.50    7.00    --   76.98 -94.00 -30.00   98
 16  \w     53.00  79.00   0.50    7.00    --   76.98 -94.00-150.00   52
 17  \w     60.00  86.00   0.50    7.00    --   76.98 -94.00 120.00   52
 18  \w     35.00  60.00   0.50    7.00    --   76.98 -94.00  60.00   50
 19  \w     43.00  84.00   0.50    7.00    --   76.98 -94.00  30.00   82
 20  \w     75.00 100.00   0.50    7.00    --   76.98-125.00   0.00   50
 21  \w     36.00  65.00   0.50    7.00    --   76.98-125.00-150.00   58
 22  \w     77.00 114.00   0.50    7.00    --   76.98  15.00 -90.00   74
 23  \w     92.00 117.00   0.50    7.00    --   76.98  15.00  60.00   50
 24  \w     58.00  84.00   0.50    7.00    --   76.98-125.00  60.00   52
 25  \w     48.00  97.00   0.50    7.00    --   76.98-125.00 150.00   98
 26  \w     37.00  86.00   0.50    7.00    --   76.98 -94.00 150.00   98
 27  \w     42.00  85.00   0.50    7.00    --   76.98 -94.00 -90.00   86
 28  \w     43.00  79.00   0.50    7.00    --   76.98 -94.00 -60.00   72
 29  \w     35.00  85.00   0.50    7.00    --   78.00 -98.00-127.08  100
 30  \w     41.00  79.00   0.50    7.00    --   81.25 -93.00  72.05   76
 31  \w     78.00 106.00   0.50    7.00    --   81.25-114.00  30.45   56
 32  \w     34.00  73.00   0.50    7.00    --   81.25-114.00  30.45   78
 33  \w     63.00 122.00   0.50    7.00    --   81.25  20.00 -51.30  118
 34  \w     78.00 129.00   0.50    7.00    --   81.25  16.00 153.29  102
 35  \w     40.00 117.00   0.50    7.00    --   81.25-132.00 124.89  154
 36  \w     86.00 114.00   0.50    7.00    --   81.25-129.00  30.29   56
 37  \w     83.00 108.00   0.50    7.00    --   81.25-126.00-129.81   50
 38  \w     43.00  76.00   0.50    7.00    --   81.25-126.00-129.81   66
 39  \w     45.00 101.00   0.50    7.00    --   81.25  12.00 128.54  112
 40  \w     60.00 129.00   0.50    7.00    --   81.25  10.00-133.94  138
 41  \w     42.00  67.00   0.50    7.00    --   81.25 -74.00 108.03   50
 42  \w     38.00  80.00   0.50    7.00    --   81.25-129.00  30.29   84
 43  \w     73.00 124.00   0.50    7.00    --   81.25-141.00 -41.41  102
 44  \w      1.00  30.00   0.50    7.00    --   -2.00  33.00-112.12   58
 45  \w     10.00  37.00   0.50    7.00    --    6.00  30.00  43.73   54
 46  \w      5.00  31.00   0.50    7.00    --    6.00  31.00 -58.25   52
 47  \w     11.00  37.00   0.50    7.00    --   10.00  30.00-145.19   52
 48  \w     10.00  37.00   0.50    7.00    --   14.00  28.00 -37.36   54
 49  \w     10.00  35.00   0.50    7.00    --   14.00  29.00 109.13   50
 50  \w     -6.00  21.00   0.50    7.00    --  -14.00  39.00  93.37   54
 51  \w     -3.00  23.00   0.50    7.00    --  -14.00  38.00 144.79   52
 52  \w    -11.00  15.00   0.50    7.00    --  -18.00  45.00  51.62   52
 53  \w     11.00  41.00   0.50    7.00    --   18.00  28.00  82.68   60
 54  \w    -51.00 -26.00   0.50    7.00    --  -42.00 -25.00-121.54   50
 55  \w    -50.00 -24.00   0.50    7.00    --  -42.00 -25.00 -40.75   52
 56  \w    -51.00 -26.00   0.50    7.00    --  -42.00 -25.00 171.42   50
 57  \w    -50.00 -24.00   0.50    7.00    --  -42.00 -25.00  35.85   52
 58  \w    -56.00 -31.00   0.50    7.00    --  -50.00 -24.00  21.83   50
 59  \w    -56.00 -31.00   0.50    7.00    --  -50.00 -24.00 -50.62   50
 60  \w    -61.00 -35.00   0.50    7.00    --  -58.00 -23.00-142.67   52
 61  \w    -62.00 -35.00   0.50    7.00    --  -58.00 -23.00 147.62   54
 62  \w    -61.00 -35.00   0.50    7.00    --  -58.00 -23.00 110.38   52
 63  \w    -62.00 -36.00   0.50    7.00    --  -58.00 -23.00  81.84   52
 64  \w    -56.00 -27.00   0.50    7.00    --  -59.37 137.00 112.00   58
 65  \w   -101.00 -76.00   0.50    7.00    --  -59.37   0.00 150.00   50
 66  \w    -99.00 -66.00   0.50    7.00    --  -59.37   0.00  30.00   66
 67  \w    -54.00 -28.00   0.50    7.00    --  -59.37 132.00 -64.00   52
 68  \w    -45.00 -18.00   0.50    7.00    --  -59.37   0.00  30.00   54
 69  \w    -71.00 -40.00   0.50    7.00    --  -66.50 -22.00-153.61   62
 70  \w    -71.00 -46.00   0.50    7.00    --  -66.50 -22.00-173.61   50
 71  \w     77.00 104.00   0.50    7.00    --   66.78  21.00 119.28   54
 72  \w     35.00  61.00   0.50    7.00    --   66.78  21.00 119.28   52
 73  \w     35.00  62.00   0.50    7.00    --   76.98-125.00 -60.00   54
 74  \w     35.00 111.00   0.50    7.00    --   76.98   0.00 120.00  152
 75  \w     36.00 116.00   0.50    7.00    --   76.98   0.00  30.00  160
 76  \w     40.00  66.00   0.50    7.00    --   76.98-125.00-180.00   52
 77  \w     90.00 116.00   0.50    7.00    --   76.98   0.00-180.00   52
 78  \w     55.00  88.00   0.50    7.00    --   76.98   0.00-180.00   66
 79  \w     35.00  61.00   0.50    7.00    --   76.98-125.00 -30.00   52
 80  \w     84.00 119.00   0.50    7.00    --   76.98   0.00 -60.00   70
 81  \w     45.00  76.00   0.50    7.00    --   76.98   0.00 -60.00   62
 82  \w     38.00  78.00   0.50    7.00    --   81.25-130.00  81.29   80
 83  \w    107.00 132.00   0.50    7.00    --   81.25  19.00-133.32   50
 84  \w     48.00 116.00   0.50    7.00    --   81.25  21.00  53.55  136
 85  \w     44.00  88.00   0.50    7.00    --   81.25  19.00-133.32   88
 86  \w     94.00 119.00   0.50    7.00    --   81.25  19.00  30.07   50
 87  \w     46.00  74.00   0.50    7.00    --   81.25  19.00  30.07   56
 88  \w    107.00 132.00   0.50    7.00    --   81.25  21.00 -66.49   50
 89  \w     51.00  86.00   0.50    7.00    --   81.25  21.00 126.22   70
 90  \w     37.00  63.00   0.50    7.00    --   81.25-114.00 124.86   52
 91  \w     50.00  77.00   0.50    7.00    --   81.25  21.00 -66.49   54
 92  \w     34.00  68.00   0.50    7.00    --   81.25-113.00 -13.75   68
 93  \w     44.00  74.00   0.50    7.00    --   81.25  20.00 -88.86   60
 94  \w     52.00  96.00   0.50    7.00    --   81.25  21.00 165.31   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1028869000
_diffrn_orient_matrix_UB_12      0.1237702000
_diffrn_orient_matrix_UB_13      0.0132641000
_diffrn_orient_matrix_UB_21      0.0004104000
_diffrn_orient_matrix_UB_22      -0.0207958000
_diffrn_orient_matrix_UB_23      0.0794361000
_diffrn_orient_matrix_UB_31      0.2287610000
_diffrn_orient_matrix_UB_32      0.0269579000
_diffrn_orient_matrix_UB_33      0.0014204000
_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  0.0370
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            35849
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.519
_diffrn_reflns_theta_min         2.310
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.609
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.791
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
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    1.204
_exptl_crystal_description       needle
_exptl_crystal_F_000             560
_exptl_crystal_size_max          0.359
_exptl_crystal_size_mid          0.022
_exptl_crystal_size_min          0.017
_refine_diff_density_max         0.983
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     417
_refine_ls_number_reflns         5658
_refine_ls_number_restraints     113
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0825
_refine_ls_R_factor_gt           0.0729
_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^)+(0.0808P)^2^+1.4400P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1820
_refine_ls_wR_factor_ref         0.1890
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4972
_reflns_number_total             5658
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03991e2.cif
_cod_data_source_block           cis_syn-(BA)-3
_cod_database_code               1567646
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C35 H38 O4'
_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
 O35-C34B \\sim O35B-C34
 with sigma of 0.02
 C37B-C36B \\sim C37-C36
 with sigma of 0.02
 O35-C36B \\sim O35B-C36
 with sigma of 0.02
 C40B-C34B \\sim C40-C34
 with sigma of 0.02
 C39B-C36B \\sim C39-C36 \\sim C38B-C36B \\sim C38-C36
 with sigma of 0.02
 C40B-C37B \\sim C40-C37
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O35B) = Uanis(O35)
4. Rigid body (RIGU) restrains
 O35, C34B, C36B, C37B, C38B, C39B, C40B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O35B, C34, C36, C37, C38, C39, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O35)=Sof(C34B)=Sof(H34B)=Sof(C36B)=Sof(C37B)=Sof(H37C)=Sof(H37D)=
 Sof(C38B)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C39B)=Sof(H39D)=Sof(H39E)=
 Sof(H39F)=Sof(C40B)=Sof(H40C)=Sof(H40D)=1-FVAR(1)
 Sof(O35B)=Sof(C34)=Sof(H34)=Sof(C36)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=
 Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=
 Sof(H40A)=Sof(H40B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C24(H24), C34(H34), C34B(H34B)
6.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C37(H37A,H37B), C37B(H37C,H37D), C40(H40A,
 H40B), C40B(H40C,H40D)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C16(H16), C17(H17), C19(H19), C20(H20)
6.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C38(H38A,H38B,
 H38C), C38B(H38D,H38E,H38F), C39(H39A,H39B,H39C), C39B(H39D,H39E,H39F)
;
_shelx_res_checksum              12652
_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 1.581
_oxdiff_exptl_absorpt_empirical_full_min 0.785