TCCA/PhSH-mediated regioselective hydroethoxylation and hydromethoxylation of allenamides <i>via</i> a radical process.
Liu, Qingsong; Jiri, Gele; She, Xingyao; Zhao, Zhigang; Li, Xiaoxiao; Organic & biomolecular chemistry 23 (2025) 7969–7974; doi:10.1039/d5ob00698h

data_7160653
_publ_section_title
;
 TCCA/PhSH-mediated regioselective hydroethoxylation and
 hydromethoxylation of allenamides <i>via</i> a radical process.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7969
_journal_page_last               7974
_journal_paper_doi               10.1039/d5ob00698h
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H21 N O3 S'
_chemical_formula_sum            'C18 H21 N O3 S'
_chemical_formula_weight         331.42
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-02-21 deposited with the CCDC.	2025-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.234(7)
_cell_length_b                   11.182(7)
_cell_length_c                   15.852(9)
_cell_measurement_reflns_used    5737
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      25.268
_cell_measurement_theta_min      2.220
_cell_volume                     1814(2)
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_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  0.0859
_diffrn_reflns_av_unetI/netI     0.0537
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            17479
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.975
_diffrn_reflns_theta_max         24.975
_diffrn_reflns_theta_min         2.570
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.192
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4983
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1440 before and 0.0928 after correction.
The Ratio of minimum to maximum transmission is 0.6683.
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    1.213
_exptl_crystal_description       plate
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.222
_refine_diff_density_min         -0.281
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 932 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(6)
_refine_ls_extinction_coef       0.041(9)
_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   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     232
_refine_ls_number_reflns         3170
_refine_ls_number_restraints     77
_refine_ls_restrained_S_all      1.163
_refine_ls_R_factor_all          0.0635
_refine_ls_R_factor_gt           0.0498
_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^)+(0.0602P)^2^+0.4472P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1362
_reflns_Friedel_coverage         0.744
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2615
_reflns_number_total             3170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00698h2.cif
_cod_data_source_block           mo_lxx_1204_0m_a
_cod_depositor_comments          'Adding full bibliography for 7160653.cif.'
_cod_database_code               7160653
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.934
_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. Restrained distances
 C9A-C17A
 1.55 with sigma of 0.01
 C9-C17
 1.55 with sigma of 0.01
 O1-C9A
 1.55 with sigma of 0.01
 O1-C8
 1.55 with sigma of 0.01
 O1-C9
 1.58 with sigma of 0.01
3. Rigid bond restraints
 C3, C2, C10, C1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C10, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C2 \\sim C10 \\sim C1 \\sim C3: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
C2 \\sim C1: within 1.7A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 1.7A
C10 \\sim C2: within 1.7A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 1.7A
Uanis(C1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C9) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C17A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq, Uanis(C17A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C9A) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C3) \\sim
Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Others
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=1-FVAR(1)
 Sof(C9)=Sof(H9A)=Sof(H9B)=FVAR(1)
 Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(2)
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C9A(H9AA,H9AB)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16)
6.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C17(H17A,H17B,H17C), C17A(H17D,H17E,H17F)
;
_olex2_submission_special_instructions 'No special instructions were received'