Total Synthesis of Purported Cephalosporolides H and I, Penisporolide B, and Their Stereoisomers.
Wang, Jian; Tong, Rongbiao; The Journal of organic chemistry 81 (2016) 4325–4339; doi:10.1021/acs.joc.6b00788

data_4036882
_publ_section_title
;
 Total Synthesis of Purported Cephalosporolides H and I, Penisporolide B,
 and Their Stereoisomers.
;
_journal_issue                   10
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4325
_journal_page_last               4339
_journal_paper_doi               10.1021/acs.joc.6b00788
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C12 H20 O5, 0.5(H2 O)'
_chemical_formula_sum            'C12 H21 O5.5'
_chemical_formula_weight         253.29
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-05-14
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                103.104(3)
_cell_angle_beta                 90.658(2)
_cell_angle_gamma                103.730(3)
_cell_formula_units_Z            12
_cell_length_a                   10.7852(3)
_cell_length_b                   13.2851(4)
_cell_length_c                   28.0787(8)
_cell_measurement_reflns_used    12650
_cell_measurement_temperature    99.9(5)
_cell_measurement_theta_max      75.3950
_cell_measurement_theta_min      4.4000
_cell_volume                     3797.4(2)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3587
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details
;
  1 omega   41.00  122.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703 -125.0000   30.0000 81

  2 omega  -49.00   35.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8203   37.0000   30.0000 84

  3 omega  -62.00   33.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8203   57.0000 -150.0000 95

  4 omega   23.00   76.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8203 -125.0000  -60.0000 53

  5 omega   45.00   93.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       40.8203 -125.0000   60.0000 48

  6 omega   36.00   98.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  -45.0000  -30.0000 62

  7 omega   80.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703   30.0000  -90.0000 98

  8 omega  108.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  125.0000 -150.0000 70

  9 omega   80.00  178.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703   30.0000    0.0000 98

 10 omega   36.00  138.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  -61.0000 -180.0000 102

 11 omega   33.00   90.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  -30.0000   90.0000 57

 12 omega   28.00  108.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.5703  -94.0000  150.0000 80

 13 omega -117.00  -25.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.8203  -37.0000   60.0000 92
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0785276000
_diffrn_orient_matrix_UB_12      -0.1096070000
_diffrn_orient_matrix_UB_13      -0.0294289000
_diffrn_orient_matrix_UB_21      0.0049183000
_diffrn_orient_matrix_UB_22      -0.0457020000
_diffrn_orient_matrix_UB_23      0.0455528000
_diffrn_orient_matrix_UB_31      -0.1246366000
_diffrn_orient_matrix_UB_32      0.0314589000
_diffrn_orient_matrix_UB_33      0.0157306000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0152
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            21154
_diffrn_reflns_theta_full        66.50
_diffrn_reflns_theta_max         67.00
_diffrn_reflns_theta_min         4.21
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.874
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET) (compiled Aug 13 2014,18:06:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1644
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.525
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     981
_refine_ls_number_reflns         13280
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.0495
_refine_ls_R_factor_gt           0.0454
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0680P)^2^+1.6250P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1183
_refine_ls_wR_factor_ref         0.1217
_reflns_number_gt                11851
_reflns_number_total             13280
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo6b00788_si_004.cif
_cod_data_source_block           jwang5cult
_cod_original_cell_volume        3797.35(19)
_cod_original_formula_sum        'C12 H21 O5.50'
_cod_database_code               4036882
_chemical_oxdiff_formula         'Ph2 O5 '
_reflns_odcompleteness_completeness 98.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O5F-C6F
 1.22 with sigma of 0.02
 C7F-C6F \\sim C8F-C7F \\sim C9E-C8F
 with sigma of 0.02
 O5E-C6E \\sim O5F-C6F
 with sigma of 0.02
 C5E-C4E \\sim C6E-C5E \\sim C7E-C6E \\sim C8E-C7E \\sim C9E-C8E
 with sigma of 0.02
3. Others
 Fixed Sof: O5E(0.85) O5F(0.15) H5EA(0.8) H5EB(0.8) H5EC(0.2) H5ED(0.2)
 C6E(0.8) C7E(0.8) H7EA(0.8) H7EB(0.8) C8E(0.8) H8EA(0.8) H8EB(0.8) C6F(0.2)
 C7F(0.2) H7FA(0.2) H7FB(0.2) C8F(0.2) H8FA(0.2) H8FB(0.2) H9E(0.8) H9EA(0.2)
4.a Free rotating group:
 O1W(H1WA,H1WB), O2W(H2WA,H2WB), O3W(H3WA,H3WB)
4.b Ternary CH refined with riding coordinates:
 C3(H3A), C4(H4A), C9(H9), C3A(H3AB), C4A(H4AB), C9A(H9A), C3B(H3BA),
 C4B(H4BA), C9B(H9B), C3C(H3CA), C4C(H4CA), C9C(H9C), C3D(H3DA), C4D(H4DA),
 C9D(H9D), C3E(H3EA), C4E(H4EA), C9E(H9E), C9E(H9EA)
4.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C7(H7A,H7B), C8(H8A,H8B), C5A(H5AA,H5AB), C7A(H7AA,H7AB),
 C8A(H8AA,H8AB), C5B(H5BA,H5BB), C7B(H7BA,H7BB), C8B(H8BA,H8BB), C5C(H5CA,H5CB),
  C7C(H7CA,H7CB), C8C(H8CA,H8CB), C5D(H5DA,H5DB), C7D(H7DA,H7DB), C8D(H8DA,
 H8DB), C5E(H5EA,H5EB), C5E(H5EC,H5ED), C7E(H7EA,H7EB), C8E(H8EA,H8EB),
 C7F(H7FA,H7FB), C8F(H8FA,H8FB)
4.d Idealised Me refined as rotating group:
 C10(H10D,H10E,H10F), C11(H11D,H11E,H11F), C12(H12D,H12E,H12F), C10A(H10G,H10H,
 H10I), C11A(H11G,H11H,H11I), C12A(H12G,H12H,H12I), C10B(H10J,H10K,H10L),
 C11B(H11J,H11K,H11L), C12B(H12J,H12K,H12L), C10C(H10M,H10N,H10O), C11C(H11M,
 H11N,H11O), C12C(H12M,H12N,H12O), C10D(H10P,H10Q,H10R), C11D(H11P,H11Q,H11R),
 C12D(H12P,H12Q,H12R), C10E(H10A,H10B,H10C), C11E(H11A,H11B,H11C), C12E(H12A,
 H12B,H12C)
4.e Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4), O3A(H3AA), O4A(H4AA), O3B(H3B), O4B(H4B), O3C(H3C), O4C(H4C),
 O3D(H3D), O4D(H4D), O3E(H3E), O4E(H4E)
;
_olex2_date_sample_data_collection 2015-02-17
_olex2_submission_special_instructions 'No special instructions were received'