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_1571159
_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         'C16 H15 N O5'
_chemical_formula_sum            'C16 H15 N O5'
_chemical_formula_weight         301.29
_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             2022-10-19
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-07-26 deposited with the CCDC.	2024-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.7584(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6843(2)
_cell_length_b                   6.33089(7)
_cell_length_c                   15.89366(18)
_cell_measurement_reflns_used    17076
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.8480
_cell_measurement_theta_min      3.3080
_cell_volume                     1433.11(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (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      100.00(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 0.972
_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     83.00 119.00   0.50    0.07    --   46.54  57.00   0.00   72
  2  \w     83.00 119.00   0.50    0.07    --   46.54  57.00  60.00   72
  3  \w     31.00 119.00   0.50    0.07    --   46.54  54.00 153.90  176
  4  \w     31.00 119.00   0.50    0.07    --   46.54  55.00  46.91  176
  5  \w     31.00 119.00   0.50    0.07    --   46.54  54.00 -51.19  176
  6  \w     31.00 119.00   0.50    0.07    --   46.54  54.00-116.64  176
  7  \w     34.00 105.00   0.50    0.30    --  106.40 -94.00   0.00  142
  8  \w     39.00 100.00   0.50    0.07    --   46.54-134.00  63.00  122
  9  \w     39.00 118.00   0.50    0.30    --  106.40-134.00  63.00  158
 10  \w     34.00 105.00   0.50    0.30    --  106.40 -94.00 120.00  142
 11  \w     34.00 105.00   0.50    0.30    --  106.40 -94.00  90.00  142
 12  \w     39.00 100.00   0.50    0.07    --   46.54-134.00-116.00  122
 13  \w     39.00 118.00   0.50    0.30    --  106.40-134.00-116.00  158
 14  \w     34.00 105.00   0.50    0.30    --  106.40 -94.00-120.00  142
 15  \w     34.00 105.00   0.50    0.30    --  106.40 -94.00-150.00  142
 16  \w     34.00 101.00   0.50    0.30    --  106.40 -77.00-120.00  134
 17  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00 -90.00   74
 18  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00   0.00   74
 19  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00  30.00   74
 20  \w     34.00  71.00   0.50    0.30    --  106.40 -61.00  60.00   74
 21  \w     89.00 178.00   0.50    0.30    --  106.40  15.00-150.00  178
 22  \w     89.00 178.00   0.50    0.30    --  106.40 134.00 130.00  178
 23  \w     91.00 178.00   0.50    0.30    --  106.40  61.00  30.00  174
 24  \w     89.00 178.00   0.50    0.30    --  106.40 134.00 -49.00  178
 25  \w    -92.00 -18.00   0.50    0.07    --  -46.54 134.00 -49.00  148
 26  \w    -85.00 -19.00   0.50    0.30    --  -91.75 125.00-180.00  132
 27  \w    -92.00 -19.00   0.50    0.30    --  -91.75 134.00 -49.00  146
 28  \w    -92.00 -18.00   0.50    0.07    --  -46.54 134.00 130.00  148
 29  \w    -92.00 -19.00   0.50    0.30    --  -91.75 134.00 130.00  146
 30  \w   -101.00 -19.00   0.50    0.30    --  -91.75  77.00 150.00  164
 31  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00 150.00   64
 32  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00   0.00   64
 33  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00 -30.00   64
 34  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00 -60.00   64
 35  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00-180.00   64
 36  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00 -90.00   64
 37  \w   -101.00 -19.00   0.50    0.30    --  -91.75  77.00 -30.00  164
 38  \w    -51.00 -19.00   0.50    0.30    --  -91.75  45.00  90.00   64
 39  \w    -30.00  29.00   0.50    0.07    --  -46.54  19.00  90.00  118
 40  \w   -119.00 -32.00   0.50    0.07    --  -46.54 -42.00 -24.02  174
 41  \w   -118.00 -83.00   0.50    0.07    --  -46.54 -57.00 150.00   70
 42  \w   -118.00 -83.00   0.50    0.07    --  -46.54 -57.00 -30.00   70
 43  \w   -118.00 -83.00   0.50    0.07    --  -46.54 -57.00 -60.00   70
 44  \w   -118.00 -83.00   0.50    0.07    --  -46.54 -57.00-180.00   70
 45  \w   -166.00 -76.00   0.50    0.30    --  -91.75 -30.00-120.00  180
 46  \w   -118.00 -68.00   0.50    0.07    --  -46.54-134.00-116.00  100
 47  \w   -161.00 -68.00   0.50    0.30    --  -91.75-134.00-116.00  186
 48  \w   -164.00-101.00   0.50    0.30    --  -91.75 -77.00 -30.00  126
 49  \w   -118.00 -68.00   0.50    0.07    --  -46.54-134.00  63.00  100
 50  \w   -118.00 -88.00   0.50    0.07    --  -46.54-125.00   0.00   60
 51  \w   -161.00 -68.00   0.50    0.30    --  -91.75-134.00  63.00  186
 52  \w   -164.00 -91.00   0.50    0.30    --  -91.75 -61.00 150.00  146
;
_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      -0.1052980000
_diffrn_orient_matrix_UB_12      0.0285234000
_diffrn_orient_matrix_UB_13      -0.0245260000
_diffrn_orient_matrix_UB_21      -0.0123279000
_diffrn_orient_matrix_UB_22      -0.2417718000
_diffrn_orient_matrix_UB_23      -0.0027209000
_diffrn_orient_matrix_UB_31      0.0213884000
_diffrn_orient_matrix_UB_32      0.0004321000
_diffrn_orient_matrix_UB_33      0.1038278000
_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  0.0329
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            30584
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.475
_diffrn_reflns_theta_min         3.324
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.877
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.621
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (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    1.396
_exptl_crystal_description       plate
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.152
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.096
_refine_diff_density_max         0.203
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     204
_refine_ls_number_reflns         2921
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0380
_refine_ls_R_factor_gt           0.0351
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0473P)^2^+0.5133P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0915
_refine_ls_wR_factor_ref         0.0943
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2657
_reflns_number_total             2921
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00316k3.cif
_cod_data_source_block           hpd614c_auto
_cod_depositor_comments
'Adding full bibliography for 1571157--1571159.cif.'
_cod_database_code               1571159
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     SB-1-65B
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.878
_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 Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C9(H9), C13(H13), C11(H11), C10(H10), C12(H12)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              95998
_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 1.224
_oxdiff_exptl_absorpt_empirical_full_min 0.826