Control of the diastereoselectivity at C(20) in the formation of C(21)-fluorinated thevinols.
Sandulenko, Irina V.; Kovaleva, Ekaterina S.; Zelentsova, Maria V.; Ambartsumyan, Asmik A.; Gorlov, Sergey N.; Danshina, Anastasia A.; Aysin, Rinat R.; Moiseev, Sergey K.; Organic & biomolecular chemistry 21 (2023) 1440–1449; doi:10.1039/d2ob02144g

data_7159090
_publ_section_title
;
 Control of the diastereoselectivity at C(20) in the formation of
 C(21)-fluorinated thevinols.
;
_journal_issue                   7
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1440
_journal_page_last               1449
_journal_paper_doi               10.1039/d2ob02144g
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C23 H23 F3 N2 O4'
_chemical_formula_sum            'C23 H23 F3 N2 O4'
_chemical_formula_weight         448.43
_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   mixed
_audit_creation_date             2022-11-03
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-03 deposited with the CCDC.	2023-01-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.814(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.0899(7)
_cell_length_b                   7.6365(5)
_cell_length_c                   26.1261(17)
_cell_measurement_reflns_used    9583
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.57
_cell_measurement_theta_min      2.38
_cell_volume                     1989.3(2)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0592
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            55164
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.996
_diffrn_reflns_theta_min         2.042
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.121
_exptl_absorpt_correction_T_max  0.5627
_exptl_absorpt_correction_T_min  0.4835
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1152 before and 0.0897 after correction.
The Ratio of minimum to maximum transmission is 0.8593.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_description       prism
_exptl_crystal_F_000             936
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.808
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.143
_refine_ls_abs_structure_details
;
 Flack x determined using 3749 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.6(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.457
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     582
_refine_ls_number_reflns         9514
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.457
_refine_ls_R_factor_all          0.1003
_refine_ls_R_factor_gt           0.0997
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2873
_refine_ls_wR_factor_ref         0.2900
_reflns_Friedel_coverage         0.865
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                9453
_reflns_number_total             9514
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob02144g2.cif
_cod_data_source_block           san436
_cod_depositor_comments
'Adding full bibliography for 7159086--7159090.cif.'
_cod_database_code               7159090
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.976
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.775(3)
 0.225(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(O3) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C19) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
4.a Riding coordinates:
 O4A(H4A), O4(H1B)
4.b Ternary CH refined with riding coordinates:
 C5A(H5A), C7A(H7A), C9A(H9A), C20A(H20A), C5(H5), C7(H7), C9(H9), C20(H20)
4.c Secondary CH2 refined with riding coordinates:
 C8A(H8AA,H8AB), C10A(H10A,H10B), C15A(H15A,H15B), C16A(H16A,H16B), C8(H8A,
 H8B), C10(H3,H4), C15(H6,H8), C16(H10,H11)
4.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C1A(H1A), C2A(H2A), C18A(H18A), C19A(H19A), C2(H2), C18(H18), C19(H19)
4.e Idealised Me refined as rotating group:
 C22A(H22B,H22A,H22C), C23A(H23A,H23B,H23C), C22(H12,H13,H14), C23(H15,H16,H17)
;
_olex2_submission_special_instructions 'No special instructions were received'