Synthesis of the ABC Substructure of Brevenal by Sequential exo-Mode Oxacyclizations of Acyclic Polyene Precursors.
Hurtak, Jessica A.; McDonald, Frank E.; Organic letters 19 (2017) 6036–6039; doi:10.1021/acs.orglett.7b02538

data_1547823
_publ_section_title
;
 Synthesis of the ABC Substructure of Brevenal by Sequential exo-Mode
 Oxacyclizations of Acyclic Polyene Precursors.
;
_journal_issue                   22
_journal_name_full               'Organic letters'
_journal_page_first              6036
_journal_page_last               6039
_journal_paper_doi               10.1021/acs.orglett.7b02538
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C16 H26 O7, 0.25(H2 O)'
_chemical_formula_sum            'C16 H26.5 O7.25'
_chemical_formula_weight         334.87
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_symmetry_space_group_name_Hall  'I 2y'
_symmetry_space_group_name_H-M   'I 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-15
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.908(8)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.911(10)
_cell_length_b                   5.551(3)
_cell_length_c                   30.35(2)
_cell_measurement_reflns_used    9891
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      28.323
_cell_measurement_theta_min      2.362
_cell_volume                     3337(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.1-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT-2014/4 (Sheldrick, 2015)'
_diffrn_ambient_temperature      110(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0417
_diffrn_reflns_av_unetI/netI     0.0677
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            16419
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.344
_diffrn_reflns_theta_min         1.170
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           35
_diffrn_source_voltage           45
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.105
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5298
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1441 before and 0.0541 after correction. The Ratio of minimum to maximum transmission is 0.7105. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.333
_exptl_crystal_description       needle
_exptl_crystal_F_000             1444
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of benzene and heptane by slow evaporation'
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.191
_exptl_crystal_size_min          0.085
_refine_diff_density_max         0.319
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 2110 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.2(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     539
_refine_ls_number_reflns         8035
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0694
_refine_ls_R_factor_gt           0.0530
_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^)+(0.0583P)^2^+0.0791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1138
_refine_ls_wR_factor_ref         0.1229
_reflns_Friedel_coverage         0.755
_reflns_Friedel_fraction_full    0.971
_reflns_Friedel_fraction_max     0.918
_reflns_number_gt                6424
_reflns_number_total             8035
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol7b02538_si_004.cif
_cod_data_source_block           jah-7-208-1_i-monocl
_cod_depositor_comments
;
Adding full bibliography for 1547823--1547824.cif.

2019-03-26
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '4(C16 H26 O7), H2 O'
_cod_original_formula_sum        'C64 H106 O29'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     1339.48
_cod_database_code               1547823
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.945
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All H(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O5B-H5B
 0.95 with sigma of 0.01
 C13B-H13A
 0.99 with sigma of 0.01
 C7-H7B
 0.99 with sigma of 0.01
 O5-H5
 0.975 with sigma of 0.01
 O1W-H1W
 0.975 with sigma of 0.01
 C10B-H10A \\sim C10B-H10B \\sim C5B-H5BA
 with sigma of 0.005
 C16B-H16B \\sim C16B-H16A \\sim C4B-H4B
 with sigma of 0.005
 C13B-H13A \\sim C13B-H13B
 with sigma of 0.002
 C9B-H9BA \\sim C9B-H9BB
 with sigma of 0.002
 C8B-H8BA \\sim C8B-H8BB
 with sigma of 0.002
 C3B-H3B \\sim C2B-H2B
 with sigma of 0.002
 C8-H8A \\sim C8-H8B \\sim C7-H7A \\sim C7-H7B \\sim C9-H9B \\sim C9-H9A
 with sigma of 0.002
 C5-H5A \\sim C2-H2 \\sim C4-H4 \\sim C3-H3
 with sigma of 0.002
 C10-H10D \\sim C10-H10C \\sim C16-H16D \\sim C16-H16C \\sim C13-H13D \\sim
C13-H13C
 with sigma of 0.002
 C12-H12F \\sim C11-H11D \\sim C11-H11E \\sim C11-H11F \\sim C12-H12D \\sim
C12-H12E \\sim C15-H15D ~
 C15-H15E \\sim C15-H15F
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uiso(H10B) = Uiso(H10A) = Uiso(H5BA)
Uiso(H16B) = Uiso(H16A) = Uiso(H4B)
Uiso(H13A) = Uiso(H13B)
Uiso(H4B) = Uiso(H3B)
Uiso(H7BA) = Uiso(H7BB)
Uiso(H8BA) = Uiso(H8BB)
Uiso(H7A) = Uiso(H7B) = Uiso(H8B) = Uiso(H9A) = Uiso(H8A) = Uiso(H9B)
Uiso(H5A) = Uiso(H4) = Uiso(H2) = Uiso(H3)
Uiso(H16D) = Uiso(H16C) = Uiso(H10D) = Uiso(H10C) = Uiso(H13D) = Uiso(H13C)
Uiso(H15E) = Uiso(H15D) = Uiso(H11D) = Uiso(H11E) = Uiso(H11F) = Uiso(H12E) =
Uiso(H12F) = Uiso(H12D) = Uiso(H15F)
Uiso(H3B) = Uiso(H2B) = Uiso(H10B) = Uiso(H10A) = Uiso(H4B) = Uiso(H5BA) =
Uiso(H7BB) = Uiso(H7BA) = Uiso(H8BA) = Uiso(H8BB) = Uiso(H9BA) = Uiso(H9BB)
4.a Idealised Me refined as rotating group:
 C12(H12D,H12E,H12F), C12B(H12A,H12B,H12C), C11B(H11A,H11B,H11C), C11(H11D,
 H11E,H11F), C15(H15D,H15E,H15F), C15B(H15A,H15B,H15C)
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id jah-7-208-1
_olex2_submission_special_instructions 'No special instructions were received'