Nickel-catalyzed hydroxymethylation with α-silicon N-methoxyphthalimides via radical Brook rearrangement
Liu, Xiao-Bo; Bilal, Muhammad; Zuo, Jiaying; Yu, Ya-Xin; Wu, Yu-Juan; Shen, Boming; Shen, Peng-Hui; Xu, Hua-Jian; Liang, Yu-Feng; Chemical Science  (2026) –; doi:10.1039/D6SC00986G

data_1576983
_publ_section_title
;
 Nickel-catalyzed hydroxymethylation with &#x3b1;-silicon
 <i>N</i>-methoxyphthalimides <i>via</i> radical Brook rearrangement.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              9653
_journal_page_last               9662
_journal_paper_doi               10.1039/d6sc00986g
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C12 H15 N O3 Si'
_chemical_formula_sum            'C12 H15 N O3 Si'
_chemical_formula_weight         249.34
_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   geom
_audit_creation_date             2025-03-03
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-03-03 deposited with the CCDC.	2026-03-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.745(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.0357(15)
_cell_length_b                   19.028(5)
_cell_length_c                   11.731(3)
_cell_measurement_reflns_used    2815
_cell_measurement_temperature    298.0
_cell_measurement_theta_max      66.070
_cell_measurement_theta_min      4.648
_cell_volume                     1345.7(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298.0
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON III'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0568
_diffrn_reflns_av_unetI/netI     0.0564
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7778
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        66.560
_diffrn_reflns_theta_max         66.560
_diffrn_reflns_theta_min         4.431
_diffrn_source_current           1.1
_diffrn_source_power             0.055
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.529
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.5220
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1264 before and 0.0733 after correction.
The Ratio of minimum to maximum transmission is 0.6934.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.231
_exptl_crystal_description       block
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.032
_exptl_crystal_size_mid          0.025
_exptl_crystal_size_min          0.014
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     157
_refine_ls_number_reflns         2344
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0499
_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^)+(0.0874P)^2^+0.0605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1396
_refine_ls_wR_factor_ref         0.1526
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1841
_reflns_number_total             2344
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00986g2.cif
_cod_data_source_block           cu_250302a_0m
_cod_depositor_comments          'Adding full bibliography for 1576983.cif.'
_cod_original_cell_volume        1345.8(5)
_cod_database_code               1576983
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.953
_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:
 C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C7(H7), C2(H2), C5(H5)
2.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              65103
_olex2_submission_special_instructions 'No special instructions were received'