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_1571157
_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         'C17 H17 N O4'
_chemical_formula_sum            'C17 H17 N O4'
_chemical_formula_weight         299.31
_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             2024-01-04
_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                72.566(2)
_cell_angle_beta                 69.8110(10)
_cell_angle_gamma                75.6020(10)
_cell_formula_units_Z            6
_cell_length_a                   12.5967(2)
_cell_length_b                   12.8747(2)
_cell_length_c                   15.6198(3)
_cell_measurement_reflns_used    21804
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      76.3230
_cell_measurement_theta_min      3.6420
_cell_volume                     2238.30(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.961
_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    --   46.75  57.00  90.00   72
  2  \w     83.00 119.00   0.50    0.07    --   46.75  57.00 120.00   72
  3  \w     89.00 178.00   0.50    0.28    --  106.69 135.00 125.00  178
  4  \w     95.00 178.00   0.50    0.28    --  106.69 125.00 150.00  166
  5  \w     83.00 119.00   0.50    0.07    --   46.75  57.00   0.00   72
  6  \w     89.00 178.00   0.50    0.28    --  106.69 134.00 -53.00  178
  7  \w    101.00 178.00   0.50    0.28    --  106.69  77.00-180.00  154
  8  \w    101.00 163.00   0.50    0.28    --  106.69  77.00 -60.00  124
  9  \w     91.00 178.00   0.50    0.28    --  106.69  30.00 -90.00  174
 10  \w     71.00 105.00   0.50    0.28    --  106.69 -94.00 -90.00   68
 11  \w     70.00 110.00   0.50    0.28    --  106.69-125.00-180.00   80
 12  \w     39.00 101.00   0.50    0.07    --   46.75-134.00-121.00  124
 13  \w     39.00 118.00   0.50    0.28    --  106.69-134.00-121.00  158
 14  \w     51.00 101.00   0.50    0.28    --  106.69 -94.00 -30.00  100
 15  \w     40.00 101.00   0.50    0.07    --   46.75-135.00  59.00  122
 16  \w     40.00 119.00   0.50    0.28    --  106.69-135.00  59.00  158
 17  \w     70.00  96.00   0.50    0.28    --  106.69-125.00 150.00   52
 18  \w     44.00  71.00   0.50    0.28    --  106.69 -61.00  90.00   54
 19  \w     34.00 106.00   0.50    0.28    --  106.69 -99.00  93.87  144
 20  \w     36.00  64.00   0.50    0.28    --  106.69 -61.00  60.00   56
 21  \w     35.00  65.00   0.50    0.28    --  106.69-125.00 150.00   60
 22  \w    -29.00  30.00   0.50    0.07    --   46.75 -19.00 150.00  118
 23  \w     35.00  69.00   0.50    0.28    --  106.69 -61.00 -30.00   68
 24  \w     34.00  71.00   0.50    0.28    --  106.69 -61.00 -90.00   74
 25  \w     34.00 106.00   0.50    0.28    --  106.69-100.00-128.32  144
 26  \w     38.00  70.00   0.50    0.28    --  106.69 -61.00-120.00   64
 27  \w     34.00  71.00   0.50    0.28    --  106.69 -61.00 -60.00   74
 28  \w     34.00 106.00   0.50    0.28    --  106.69 -99.00-159.41  144
 29  \w     35.00  67.00   0.50    0.28    --  106.69 -61.00-150.00   64
 30  \w    -92.00 -18.00   0.50    0.07    --  -46.75 134.00 -53.00  148
 31  \w    -51.00 -16.00   0.50    0.28    --  -88.50  45.00   0.00   70
 32  \w    -51.00 -16.00   0.50    0.28    --  -88.50  45.00 -60.00   70
 33  \w    -92.00 -18.00   0.50    0.28    --  -88.50 134.00 -53.00  148
 34  \w    -94.00 -18.00   0.50    0.07    --  -46.75 135.00 125.00  152
 35  \w    -94.00 -18.00   0.50    0.28    --  -88.50 135.00 125.00  152
 36  \w   -119.00 -83.00   0.50    0.07    --  -46.75 -57.00  60.00   72
 37  \w   -119.00 -67.00   0.50    0.07    --  -46.75-135.00  59.00  104
 38  \w   -119.00 -83.00   0.50    0.07    --  -46.75 -57.00 150.00   72
 39  \w   -160.00 -67.00   0.50    0.28    --  -88.50-135.00  59.00  186
 40  \w   -119.00 -83.00   0.50    0.07    --  -46.75 -57.00 -60.00   72
 41  \w   -119.00 -68.00   0.50    0.07    --  -46.75-134.00-121.00  102
 42  \w   -119.00 -83.00   0.50    0.07    --  -46.75 -57.00-150.00   72
 43  \w   -160.00 -68.00   0.50    0.28    --  -88.50-134.00-121.00  184
 44  \w   -160.00 -78.00   0.50    0.28    --  -88.50 -56.00-113.67  164
 45  \w   -160.00-101.00   0.50    0.28    --  -88.50 -77.00 -90.00  118
 46  \w   -160.00 -73.00   0.50    0.28    --  -88.50 -55.00 116.06  174
 47  \w   -160.00 -91.00   0.50    0.28    --  -88.50 -61.00 150.00  138
;
_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      -0.0225540000
_diffrn_orient_matrix_UB_12      -0.1098875000
_diffrn_orient_matrix_UB_13      -0.0051886000
_diffrn_orient_matrix_UB_21      -0.0395058000
_diffrn_orient_matrix_UB_22      -0.0353319000
_diffrn_orient_matrix_UB_23      0.1079927000
_diffrn_orient_matrix_UB_31      -0.1239714000
_diffrn_orient_matrix_UB_32      0.0532137000
_diffrn_orient_matrix_UB_33      0.0002560000
_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  0.0360
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            42637
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.589
_diffrn_reflns_theta_min         3.101
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.785
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.653
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (Rigaku Oxford Diffraction, 2019)
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    1.332
_exptl_crystal_description       plate
_exptl_crystal_F_000             948
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.088
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.800
_refine_diff_density_min         -0.736
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     594
_refine_ls_number_reflns         9064
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0565
_refine_ls_R_factor_gt           0.0512
_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^)+(0.0400P)^2^+1.8000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1191
_refine_ls_wR_factor_ref         0.1228
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8008
_reflns_number_total             9064
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00316k3.cif
_cod_data_source_block           hpd462b
_cod_depositor_comments
'Adding full bibliography for 1571157--1571159.cif.'
_cod_database_code               1571157
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     'LDA 05-324P'
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.898
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C29-C30 = C26-C27 = C27-C28
 1.37 with sigma of 0.02
 C29-C28
 1.38 with sigma of 0.02
 C30-C31 = C31-C26
 1.36 with sigma of 0.02
 C30-C26
 2.36 with sigma of 0.04
 C29-C31 = C31-C27 = C26-C28
 2.37 with sigma of 0.04
 C29-C27
 2.38 with sigma of 0.04
 C29-C27 \\sim C29-C31 \\sim C27-C31 \\sim C26-C30 \\sim C26-C28 \\sim C28-C30
 with sigma of 0.04
 C29-C30 \\sim C30-C31 \\sim C31-C26 \\sim C26-C27 \\sim C27-C28 \\sim C28-C29
 with sigma of 0.02
3. Restrained planarity
 C29, C30, C31, C26, C27, C28
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C17B) = Uanis(C16A) = Uanis(C16B) = Uanis(C17A)
Uanis(O4) = Uanis(C15)
Uanis(C27) = Uanis(C26) = Uanis(C31) = Uanis(C30) = Uanis(C29) = Uanis(C28)
5. Others
 Fixed Sof: C16A(0.6) H16A(0.6) H16B(0.6) C34A(0.6) H34A(0.6) H34B(0.6)
 H34C(0.6) C33A(0.6) H33A(0.6) H33B(0.6) C17A(0.6) H17A(0.6) H17B(0.6)
 H17C(0.6) C17B(0.4) H17D(0.4) H17E(0.4) H17F(0.4) C16B(0.4) H16C(0.4)
 H16D(0.4) C33B(0.4) H33C(0.4) H33D(0.4) C34B(0.4) H34D(0.4) H34E(0.4)
 H34F(0.4) O3B(0.4) O3A(0.6)
6.a Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C50(H50A,H50B), C24(H24A,H24B), C7(H7A,H7B), C16A(H16A,H16B),
 C33A(H33A,H33B), C16B(H16C,H16D), C33B(H33C,H33D)
6.b Aromatic/amide H refined with riding coordinates:
 N3(H3A), N1(H1), N2(H2), C44(H44), C48(H48), C37(H37), C47(H47), C46(H46),
 C45(H45), C20(H20), C3(H3), C10(H10), C14(H14), C11(H11), C13(H13), C12(H12),
 C29(H29), C30(H30), C31(H31), C27(H27), C28(H28)
6.c Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C51(H51A,H51B,H51C), C25(H25A,H25B,H25C), C8(H8A,H8B,
 H8C), C34A(H34A,H34B,H34C), C17A(H17A,H17B,H17C), C17B(H17D,H17E,H17F),
 C34B(H34D,H34E,H34F)
;
_shelx_res_checksum              68347
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.272
_oxdiff_exptl_absorpt_empirical_full_min 0.750