Total Synthesis of the GRP78-Downregulatory Macrolide (+)-Prunustatin A, the Immunosuppressant (+)-SW-163A, and a JBIR-04 Diastereoisomer That Confirms JBIR-04 Has Nonidentical Stereochemistry to (+)-Prunustatin A.
Manaviazar, Soraya; Nockemann, Peter; Hale, Karl J.; Organic letters 18 (2016) 2902–2905; doi:10.1021/acs.orglett.6b01235

data_1543362
_publ_section_title
;
 Total Synthesis of the GRP78-Downregulatory Macrolide (+)-Prunustatin A,
 the Immunosuppressant (+)-SW-163A, and a JBIR-04 Diastereoisomer That
 Confirms JBIR-04 Has Nonidentical Stereochemistry to (+)-Prunustatin A.
;
_journal_issue                   12
_journal_name_full               'Organic letters'
_journal_page_first              2902
_journal_page_last               2905
_journal_paper_doi               10.1021/acs.orglett.6b01235
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C31 H43 N O11, C2.5, 0.56(O)'
_chemical_formula_sum            'C33 H43 N O12'
_chemical_formula_weight         645.68
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-05-24
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.16 svn.r3265 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   27.6917(6)
_cell_length_b                   14.8522(2)
_cell_length_c                   8.87923(16)
_cell_measurement_reflns_used    19952
_cell_measurement_temperature    292.41(10)
_cell_measurement_theta_max      72.7040
_cell_measurement_theta_min      4.9470
_cell_volume                     3651.87(11)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      292.41(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0509
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
  1 omega    1.00   73.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327  -99.0000 -150.0000 72

  2 omega    1.00   73.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327  -99.0000   60.0000 72

  3 omega    1.00   73.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327  -99.0000  -60.0000 72

  4 omega    1.00   73.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327  -99.0000    0.0000 72

  5 omega  -32.00   54.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327  -38.0000   60.0000 86

  6 omega    1.00   73.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327  -99.0000  120.0000 72

  7 omega   23.00   89.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327 -125.0000  -90.0000 66

  8 omega   39.00   91.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287  -30.0000   90.0000 52

  9 omega   39.00   91.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287  -30.0000  -90.0000 52

 10 omega   40.00   98.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287  -45.0000  -30.0000 58

 11 omega   91.00  173.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287   59.0000   83.0000 82

 12 omega   39.00   91.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287  -30.0000 -180.0000 52

 13 omega   40.00   98.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287  -45.0000  150.0000 58

 14 omega   38.00  177.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287    0.0000   60.0000 139

 15 omega   11.00  103.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327   77.0000 -150.0000 92

 16 omega   21.00  102.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327   57.0000    0.0000 81

 17 omega   11.00  103.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327   77.0000  150.0000 92

 18 omega   21.00  102.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327   57.0000  120.0000 81

 19 omega   11.00  103.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327   77.0000  -90.0000 92

 20 omega   11.00  103.00   1.0000    4.5600
omega____ theta____ kappa____ phi______ frames
    -       36.2327   77.0000   30.0000 92

 21 omega   75.00  176.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287   15.0000  -90.0000 101

 22 omega   82.00  147.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287   77.0000  -60.0000 65

 23 omega   40.00   98.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287  -45.0000   30.0000 58

 24 omega   75.00  176.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287   15.0000 -180.0000 101

 25 omega   39.00  109.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287  -95.0000  -60.0000 70

 26 omega   38.00  116.00   1.0000   18.2300
omega____ theta____ kappa____ phi______ frames
    -      107.3287 -111.0000  150.0000 78
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0363672000
_diffrn_orient_matrix_UB_12      -0.0261864000
_diffrn_orient_matrix_UB_13      0.1237985000
_diffrn_orient_matrix_UB_21      0.0106388000
_diffrn_orient_matrix_UB_22      0.1003635000
_diffrn_orient_matrix_UB_23      0.0289908000
_diffrn_orient_matrix_UB_31      -0.0406919000
_diffrn_orient_matrix_UB_32      0.0029089000
_diffrn_orient_matrix_UB_33      0.1181010000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0611
_diffrn_reflns_av_unetI/netI     0.0315
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            33607
_diffrn_reflns_theta_full        72.73
_diffrn_reflns_theta_max         72.73
_diffrn_reflns_theta_min         4.37
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.747
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55280
_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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1376
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.021
_refine_diff_density_min         -0.441
_refine_diff_density_rms         0.118
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     411
_refine_ls_number_reflns         7199
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0885
_refine_ls_R_factor_gt           0.0861
_refine_ls_shift/su_max          0.032
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1718P)^2^+3.3415P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2445
_refine_ls_wR_factor_ref         0.2485
_reflns_number_gt                6897
_reflns_number_total             7199
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ol6b01235_si_003.cif
_cod_data_source_block           exp_142sm19123
_cod_depositor_comments
'Adding full bibliography for 1543360--1543363.cif.'
_cod_original_cell_volume        3651.88(11)
_cod_database_code               1543362
_chemical_oxdiff_formula         'C H O N'
_chemical_oxdiff_usercomment     Karl
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(O00C)=Sof(C0)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(H3C)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(O00B)=Sof(C014)=Sof(C016)=Sof(H01M)=Sof(H01N)=Sof(H01O)=Sof(C017)=
 Sof(H01P)=Sof(H01Q)=Sof(H01R)=Sof(C018)=Sof(H01S)=Sof(H01T)=Sof(H01U)=FVAR(1)
 Fixed Sof: O2(0.25)
3.a Ternary CH refined with riding coordinates:
 C00I(H00I), C00N(H00N), C00O(H00O), C00Q(H00Q), C00T(H00T), C00W(H00W)
3.b Secondary CH2 refined with riding coordinates:
 C00M(H00A,H00B), C00P(H00D,H00E)
3.c Aromatic/amide H refined with riding coordinates:
 N00C(H00C), C00G(H00G), C00R(H00R), C00V(H00V), C00X(H00X), C00Z(H00Z)
3.d Idealised Me refined as rotating group:
 C00U(H00F,H00H,H00J), C00Y(H00K,H00L,H00M), C010(H01A,H01B,H01C), C011(H01D,
 H01E,H01F), C012(H01G,H01H,H01I), C013(H01J,H01K,H01L), C016(H01M,H01N,H01O),
 C017(H01P,H01Q,H01R), C018(H01S,H01T,H01U), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C),
 C1AA(H1AA,H1AB,H1AC)
;
_olex2_submission_special_instructions 'No special instructions were received'