Diastereoselective C(sp3)–H acetoxylation of phosphoramidites
Mondal, Anirban; Dašková, Vanda; Chen, Xiaobing; Thiel, Niklas O.; Alachouzos, Georgios; Feringa, Ben L.; Chemical Communications 61 (2025) 6510–6513; doi:10.1039/D5CC00550G

data_7134385
_publ_section_title
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 Diastereoselective C(sp3)--H acetoxylation of phosphoramidites
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_journal_issue                   35
_journal_name_full               'Chemical Communications'
_journal_page_first              6510
_journal_page_last               6513
_journal_paper_doi               10.1039/D5CC00550G
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C35 H36 N O5 P, C H2 Cl2'
_chemical_formula_sum            'C36 H38 Cl2 N O5 P'
_chemical_formula_weight         666.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
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_audit_update_record
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2023-08-30 deposited with the CCDC.	2025-03-31 downloaded from the CCDC.
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_cell_angle_alpha                90
_cell_angle_beta                 106.627(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.6352(9)
_cell_length_b                   6.4448(4)
_cell_length_c                   20.9210(16)
_cell_measurement_reflns_used    9893
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      28.32
_cell_measurement_theta_min      2.99
_cell_volume                     1632.4(2)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 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_temperature      100.00
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1007
_diffrn_reflns_av_unetI/netI     0.0442
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            107515
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.248
_diffrn_reflns_theta_min         2.986
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.292
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6994
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0761 before and 0.0700 after correction.
The Ratio of minimum to maximum transmission is 0.9380.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_description       plate
_exptl_crystal_F_000             700
_exptl_crystal_size_max          0.203
_exptl_crystal_size_mid          0.037
_exptl_crystal_size_min          0.026
_refine_diff_density_max         0.600
_refine_diff_density_min         -0.690
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 2993 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_coef       0.0059(18)
_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   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         8838
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0601
_refine_ls_R_factor_gt           0.0456
_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^)+(0.0452P)^2^+1.0319P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1088
_reflns_Friedel_coverage         0.844
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                7517
_reflns_number_total             8838
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00550g2.cif
_cod_data_source_block           mo_cns_ch_activation_adamantyl_a
_cod_depositor_comments          'Adding full bibliography for 7134385.cif.'
_cod_database_code               7134385
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.943
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C00U(H00U), C00X(H00X), C00Z(H00Z), C010(H010), C011(H011), C013(H013)
1.b Secondary CH2 refined with riding coordinates:
 C00K(H00A,H00F), C00O(H00G,H00H), C00T(H00I,H00K), C00V(H00N,H00O), C015(H01D,
 H01E), C018(H01I,H01J), C019(H01K,H01L)
1.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00B(H00B), C00C(H00C), C00D(H00D), C00E(H00E), C00J(H00J),
 C00L(H00L), C00M(H00M), C00P(H00P), C00Q(H00Q), C00S(H00S), C00W(H00W)
1.d Idealised Me refined as rotating group:
 C012(H01A,H01B,H01C), C017(H01F,H01G,H01H)
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_shelx_res_checksum              81361
_shelx_hkl_checksum              94175
_olex2_submission_special_instructions 'No special instructions were received'