Total syntheses of ent-hypocoprin A and ent-hypocoprin B
Ota, Koichiro; Watanabe, Taiki; Igarashi, Shuntaro; Okazaki, Shinnosuke; Kamaike, Kazuo; Miyaoka, Hiroaki; RSC Advances 12 (2022) 16576–16580; doi:10.1039/D2RA02891C

data_7245035
_publ_section_title
;
 Total syntheses of ent-hypocoprin A and ent-hypocoprin B
;
_journal_issue                   26
_journal_name_full               'RSC Advances'
_journal_page_first              16576
_journal_page_last               16580
_journal_paper_doi               10.1039/D2RA02891C
_journal_volume                  12
_journal_year                    2022
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C15 H26 O2'
_chemical_formula_sum            'C15 H26 O2'
_chemical_formula_weight         238.36
_space_group_crystal_system      hexagonal
_space_group_IT_number           172
_space_group_name_Hall           'P 64'
_space_group_name_H-M_alt        'P 64'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2022-02-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-02-04 deposited with the CCDC.	2022-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            12
_cell_length_a                   30.947(2)
_cell_length_b                   30.947(2)
_cell_length_c                   6.2208(7)
_cell_measurement_reflns_used    9973
_cell_measurement_temperature    90
_cell_measurement_theta_max      22.00
_cell_measurement_theta_min      2.63
_cell_volume                     5159.6(7)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX2 ver.2014/11(Bruker AXS Inc., 2014)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      90
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 8.333
_diffrn_detector_type            'Bruker SMART APEX II ULTRA'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'Bruker SMART APEX II ULTRA'
_diffrn_measurement_device_type  'Bruker SMART APEX II ULTRA'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    '0.5 mm  '
_diffrn_radiation_monochromator  'Bruker Helios multilayered confocal mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0541
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -6
_diffrn_reflns_number            93471
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        23.263
_diffrn_reflns_theta_max         23.263
_diffrn_reflns_theta_min         1.316
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Bruker TXS fine-focus Turbo X-ray Source'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.059
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9104
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1372 before and 0.0592 after correction.
The Ratio of minimum to maximum transmission is 0.9104.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.921
_exptl_crystal_description       needle
_exptl_crystal_F_000             1584
_exptl_crystal_recrystallization_method
'The single crystals were dissolved in dichloromethane, 1 drops of toluene were added, and then hexane was added dropwise.'
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.061
_refine_diff_density_max         0.679
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.107
_refine_ls_abs_structure_details
;
 Flack x determined using 2020 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     319
_refine_ls_number_reflns         4918
_refine_ls_number_restraints     421
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.1090
_refine_ls_R_factor_gt           0.1075
_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^)+(0.1811P)^2^+14.3687P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2873
_refine_ls_wR_factor_ref         0.2889
_reflns_Friedel_coverage         0.802
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4794
_reflns_number_total             4918
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ra02891c2.cif
_cod_data_source_block           ha-16-1_a
_cod_original_cell_volume        5159.6(10)
_cod_database_code               7245035
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.983
_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. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim O1 \\sim O2
\\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A
\\sim C9A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A
\\sim O1A \\sim O2A: within 2A with sigma of 0.005 and sigma for terminal atoms
of 0.002 within 2A
Uanis(C1A) \\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C11A)
\\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C10A) \\sim Ueq,
Uanis(C4A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C14A)
\\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq,
Uanis(C6A) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C6) \\sim
Ueq, Uanis(O2) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.009 and sigma
for terminal atoms of 0.01
3.a Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C9(H9), C1A(H1AA), C7A(H7A), C9A(H9A)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C8(H8A,H8B), C11(H11A,H11B), C4A(H4AA,H4AB),
 C5A(H5AA,H5AB), C8A(H8AA,H8AB), C11A(H11C,H11D)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C3A(H3A)
3.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C12A(H12D,H12E,H12F), C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F),
 C15A(H15D,H15E,H15F)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1A), O2(H2), O1A(H1AB), O2A(H2A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              58852
_shelx_fab_checksum              47120
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MiTeGEN MicroMounts in  perfluoropolyether oil'
_olex2_submission_special_instructions 'No special instructions were received'