Synthesis and Separation of Two Stereoisomers of Deuterated Tetrasubstituted Allylic Alcohols via Consecutive Dual 1,2-Metallate Shifts
Li, Puhui; Yu, Yajun; Ma, Xingxing; Song, Qiuling; Chemical Science  (2025) –; doi:10.1039/D5SC06886J

data_1576386
_publ_section_title
;
 Synthesis and Separation of Two Stereoisomers of Deuterated
 Tetrasubstituted Allylic Alcohols via Consecutive Dual 1,2-Metallate
 Shifts
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC06886J
_journal_year                    2025
_chemical_formula_moiety         'C20 H23 Br O2'
_chemical_formula_sum            'C20 H23 Br O2'
_chemical_formula_weight         375.29
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2022-12-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2023-03-12 deposited with the CCDC.	2025-12-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.476(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.565(9)
_cell_length_b                   5.361(2)
_cell_length_c                   15.030(6)
_cell_measurement_reflns_used    8004
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      24.033
_cell_measurement_theta_min      2.799
_cell_volume                     1729.7(12)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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  0.0843
_diffrn_reflns_av_unetI/netI     0.0598
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            33705
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.303
_diffrn_reflns_theta_min         2.723
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.384
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5516
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1066 before and 0.0692 after correction.
The Ratio of minimum to maximum transmission is 0.7399.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.441
_exptl_crystal_description       block
_exptl_crystal_F_000             776
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.324
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     211
_refine_ls_number_reflns         3835
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0399
_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^)+(0.0254P)^2^+1.5005P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0781
_refine_ls_wR_factor_ref         0.0893
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2625
_reflns_number_total             3835
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06886j2.cif
_cod_data_source_block           lph1823d_0m
_cod_database_code               1576386
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.763
_shelx_estimated_absorpt_t_min   0.716
_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, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C006(H00A,H00B), C009(H00C,H00D), C00A(H00E,H00F), C00E(H00I,H00J)
2.b Aromatic/amide H refined with riding coordinates:
 C004(H004), C00B(H00G), C00C(H00H), C00F(H00K), C00G(H00L), C00J(H00M),
 C00K(H00N), C00L(H00O)
2.c Idealised Me refined as rotating group:
 C00M(H00P,H00Q,H00R), C00N(H00S,H00T,H00U)
2.d Idealised tetrahedral OH refined as rotating group:
 O003(H003)
;
_shelx_res_checksum              26015
_olex2_submission_special_instructions 'No special instructions were received'