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_7159088
_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 syn
_chemical_formula_moiety         'C26 H32 F3 N O4'
_chemical_formula_sum            'C26 H32 F3 N O4'
_chemical_formula_weight         479.52
_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     direct
_audit_creation_date             2022-11-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-21 deposited with the CCDC.	2023-01-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.581(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.0711(13)
_cell_length_b                   10.670(2)
_cell_length_c                   15.423(3)
_cell_measurement_reflns_used    9893
_cell_measurement_temperature    120
_cell_measurement_theta_max      29.58
_cell_measurement_theta_min      2.36
_cell_volume                     1143.9(4)
_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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD 1K area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0225
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            13376
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.001
_diffrn_reflns_theta_min         2.334
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.109
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6748
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1297 before and 0.0626 after correction.
The Ratio of minimum to maximum transmission is 0.9047.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       prism
_exptl_crystal_F_000             508
_exptl_crystal_recrystallization_method 'crystallized from ???'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.203
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 2319 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.3(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     396
_refine_ls_number_reflns         6467
_refine_ls_number_restraints     119
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0414
_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^)+(0.0539P)^2^+0.2041P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1015
_refine_ls_wR_factor_ref         0.1102
_reflns_Friedel_coverage         0.861
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.946
_reflns_number_gt                5535
_reflns_number_total             6467
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob02144g2.cif
_cod_data_source_block           a_CCDC1
_cod_depositor_comments
'Adding full bibliography for 7159086--7159090.cif.'
_cod_database_code               7159088
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.974
_olex2_refinement_description
;
1. Restrained distances
 C7-C20B
 1.5 with sigma of 0.01
 C22B-C20B
 1.5 with sigma of 0.01
2. Rigid body (RIGU) restrains
 C20B, C22B, H22A, O4, C23, H23A, H23B, C24, H24A, H24B, H24C, C21A, F3A, F1A,
 F2A, H22B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(H7B)=Sof(C21B)=Sof(O4')=Sof(H4')=Sof(C23')=
 Sof(H23C)=Sof(H23D)=Sof(C24')=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C22A)=
 Sof(H22C)=Sof(H22D)=Sof(C20A)=1-FVAR(1)
 Sof(H7A)=Sof(C20B)=Sof(C22B)=Sof(H22A)=Sof(H22B)=Sof(O4)=Sof(H4)=Sof(C23)=
 Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C21A)=Sof(F3A)=
 Sof(F1A)=Sof(F2A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C5(H5), C7(H7A), C9(H9)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C15(H15A,H15B), C16(H16A,H16B), C22B(H22A,H22B),
 C23(H23A,H23B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C18(H18), C19(H19)
4.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C24(H24A,H24B,
 H24C)
4.e Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_shelx_res_checksum              70170
_olex2_exptl_crystal_mounting_method 'mounted on a needle'
_olex2_submission_special_instructions 'No special instructions were received'