The “cesium effect” magnified: exceptional chemoselectivity in cesium ion mediated nucleophilic reactions
Biswas, Soumen; Hughes, William B.; De Angelis, Luca; Haug, Graham C.; Trevino, Ramon; Fremin, Seth O.; Arman, Hadi D.; Larionov, Oleg V.; Doyle, Michael P.; Chemical Science 15 (2024) 5277–5283; doi:10.1039/D4SC00316K

data_1571158
_publ_section_title
;
 The &#x201C;cesium effect&#x201D; magnified: exceptional chemoselectivity
 in cesium ion mediated nucleophilic reactions
;
_journal_issue                   14
_journal_name_full               'Chemical Science'
_journal_page_first              5277
_journal_page_last               5283
_journal_paper_doi               10.1039/D4SC00316K
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C29 H26 N2 O5'
_chemical_formula_sum            'C29 H26 N2 O5'
_chemical_formula_weight         482.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-04
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-01-05 deposited with the CCDC.	2024-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.0934(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.83436(15)
_cell_length_b                   11.10289(10)
_cell_length_c                   20.5729(2)
_cell_measurement_reflns_used    18475
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.1120
_cell_measurement_theta_min      4.5320
_cell_volume                     2986.18(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.79a (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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(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 0.955
_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     91.00 178.00   0.50    0.30    --  106.40  34.00 -50.00  174
  2  \w     31.00  95.00   0.50    0.08    --   46.79  53.00  40.47  128
  3  \w     32.00 121.00   0.50    0.08    --   46.79  34.00 -50.00  178
  4  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00-180.00   74
  5  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00-150.00   74
  6  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00-120.00   74
  7  \w     34.00 101.00   0.50    0.30    --  106.40 -77.00   0.00  134
  8  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00  90.00   74
  9  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00 150.00   74
 10  \w    -27.00  40.00   0.50    0.08    --   46.79 -34.00 151.00  134
 11  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00   0.00   74
 12  \w     36.00 105.00   0.50    0.30    --  106.40 -98.00 -35.52  138
 13  \w    -30.00  29.00   0.50    0.08    --  -46.79  19.00  90.00  118
 14  \w    -40.00  28.00   0.50    0.08    --  -46.79  34.00 -50.00  136
 15  \w     34.00 105.00   0.50    0.30    --  106.40 -94.00-180.00  142
 16  \w    -71.00 -19.00   0.50    0.30    --  -91.75  61.00 120.00  104
 17  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00 150.00   64
 18  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00 120.00   64
 19  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00  90.00   64
 20  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00  30.00   64
 21  \w   -166.00 -76.00   0.50    0.30    --  -91.75 -34.00 151.00  180
 22  \w   -164.00-101.00   0.50    0.30    --  -91.75 -77.00  90.00  126
 23  \w   -121.00 -32.00   0.50    0.08    --  -46.79 -34.00 151.00  178
 24  \w   -164.00-100.00   0.50    0.30    --  -91.75 -94.00 -90.00  128
 25  \w    -85.00 -13.00   0.50    0.08    --  -46.79 125.00-180.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0327711000
_diffrn_orient_matrix_UB_12      0.0383444000
_diffrn_orient_matrix_UB_13      0.0760993000
_diffrn_orient_matrix_UB_21      0.1023703000
_diffrn_orient_matrix_UB_22      0.0467322000
_diffrn_orient_matrix_UB_23      -0.0046956000
_diffrn_orient_matrix_UB_31      -0.0482962000
_diffrn_orient_matrix_UB_32      0.1248965000
_diffrn_orient_matrix_UB_33      -0.0216141000
_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  0.0315
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29230
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.375
_diffrn_reflns_theta_min         3.381
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.601
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.487
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.79a (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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.073
_exptl_crystal_description       plate
_exptl_crystal_F_000             1016
_exptl_crystal_size_max          0.237
_exptl_crystal_size_mid          0.171
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.204
_refine_diff_density_min         -0.337
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     359
_refine_ls_number_reflns         5981
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0475
_refine_ls_R_factor_gt           0.0438
_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^)+(0.0679P)^2^+1.1647P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1244
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5335
_reflns_number_total             5981
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00316k3.cif
_cod_data_source_block           hpd750_try2_auto
_cod_depositor_comments
'Adding full bibliography for 1571157--1571159.cif.'
_cod_original_cell_volume        2986.19(6)
_cod_database_code               1571158
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     'Soumen Mystery'
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.871
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H28C,H28D,H1} of C28B, All C(H,H) groups
 At 1.5 times of:
  {H20A,H20B,H20C} of C20, {H8A,H8B,H8C} of C8, {H29A,H29B,H29C} of C29A,
  {H29D,H29E,H29F} of C29B
2. Others
 Fixed Sof: O5A(0.75) C28A(0.75) H28A(0.75) H28B(0.75) C29A(0.75) H29A(0.75)
 H29B(0.75) H29C(0.75) C29B(0.25) H29D(0.25) H29E(0.25) H29F(0.25) O5B(0.25)
 C28B(0.25) H28C(0.25) H28D(0.25)
3.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C28A(H28A,H28B), C28B(H28C,H28D)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C10(H10), C14(H14), C11(H11), C17(H17), C12(H12), C22(H22), C13(H13),
 C26(H26), C23(H23), C24(H24), C25(H25)
3.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C8(H8A,H8B,H8C), C29A(H29A,H29B,H29C), C29B(H29D,H29E,
 H29F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              53873
_shelx_fab_checksum              93006
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.876
_oxdiff_exptl_absorpt_empirical_full_min 0.613