Total Synthesis of the Marine Alkaloid Discoipyrrole C via the MoOPH-Mediated Oxidation of a 2,3,5-Trisubstituted Pyrrole.
Yan, Qiao; Ma, Xiang; Banwell, Martin G.; Ward, Jas S.; Journal of natural products 80 (2017) 3305–3313; doi:10.1021/acs.jnatprod.7b00872

data_1548283
_publ_section_title
;
 Total Synthesis of the Marine Alkaloid Discoipyrrole C via the
 MoOPH-Mediated Oxidation of a 2,3,5-Trisubstituted Pyrrole.
;
_journal_issue                   12
_journal_name_full               'Journal of natural products'
_journal_page_first              3305
_journal_page_last               3313
_journal_paper_doi               10.1021/acs.jnatprod.7b00872
_journal_volume                  80
_journal_year                    2017
_chemical_formula_moiety         'C44 H48 N2 O4, 2(C3 H6 O)'
_chemical_formula_sum            'C50 H60 N2 O6'
_chemical_formula_weight         785.00
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-08-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.220(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.2834(19)
_cell_length_b                   10.8405(9)
_cell_length_c                   24.0533(13)
_cell_measurement_reflns_used    3417
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      69.8190
_cell_measurement_theta_min      2.8980
_cell_volume                     5028.1(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w   -102.00  29.00   1.00   20.00    --  -36.03   0.00-180.00  131
  2  \w    -88.00 -24.00   1.00   20.00    --  -36.03 125.00  30.00   64
  3  \w     19.00 103.00   1.00   20.00    --   36.03  57.00   0.00   84
  4  \w    -21.00  53.00   1.00   20.00    --   36.03 -57.00 150.00   74
  5  \w     23.00  89.00   1.00   20.00    --   36.03-125.00 -60.00   66
  6  \w     44.00 109.00   1.00  100.00    --  107.33 -95.00 -90.00   65
  7  \w     40.00 122.00   1.00  100.00    --  107.33 -45.00-120.00   82
  8  \w     41.00 125.00   1.00  100.00    --  107.33 -45.00 150.00   84
  9  \w    109.00 164.00   1.00  100.00    --  107.33  45.00 120.00   55
 10  \w     60.00 109.00   1.00  100.00    --  107.33 -95.00 150.00   49
 11  \w     42.00 125.00   1.00  100.00    --  107.33 -45.00 -30.00   83
 12  \w     45.00 125.00   1.00  100.00    --  107.33 -45.00  60.00   80
 13  \w     37.00 115.00   1.00  100.00    --  107.33-111.00  30.00   78
 14  \w     48.00 107.00   1.00  100.00    --  107.33 -77.00  30.00   59
 15  \w     39.00 172.00   1.00  100.00    --  107.33   0.00  90.00  133
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0735728000
_diffrn_orient_matrix_UB_12      0.0132684000
_diffrn_orient_matrix_UB_13      -0.0240441000
_diffrn_orient_matrix_UB_21      0.0036264000
_diffrn_orient_matrix_UB_22      -0.1405609000
_diffrn_orient_matrix_UB_23      -0.0089280000
_diffrn_orient_matrix_UB_31      -0.0309358000
_diffrn_orient_matrix_UB_32      0.0157002000
_diffrn_orient_matrix_UB_33      -0.0587149000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0527
_diffrn_reflns_av_unetI/netI     0.0673
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            27083
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.225
_diffrn_reflns_theta_min         2.932
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.533
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39030
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.037
_exptl_crystal_description       needle
_exptl_crystal_F_000             1688
_exptl_crystal_size_max          0.439
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.038
_refine_diff_density_max         0.470
_refine_diff_density_min         -0.517
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     615
_refine_ls_number_reflns         9690
_refine_ls_number_restraints     201
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.1692
_refine_ls_R_factor_gt           0.1138
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3275
_refine_ls_wR_factor_ref         0.3803
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4982
_reflns_number_total             9690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np7b00872_si_002.cif
_cod_data_source_block           YQ-11-P4_2_scale_sq_compound_11
_cod_depositor_comments
'Adding full bibliography for 1548282--1548286.cif.'
_cod_database_code               1548283
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C203-C201 = C1B-C1A = C202-C201 = C1C-C1A
 1.46 with sigma of 0.01
 O4-C1A = O201-C201
 1.2 with sigma of 0.01
 H10F_$1-H52D
 -2.15 with sigma of 0.01
 C36B-C35 = C36A-C35
 1.5 with sigma of 0.01
 C36A-C38A = C36A-C37A = C36B-C37B = C36B-C38B
 1.54 with sigma of 0.01
 O201-C202
 2.34 with sigma of 0.02
 O201-C203
 2.34 with sigma of 0.02
 O4-C1B
 2.34 with sigma of 0.02
 O4-C1C
 2.34 with sigma of 0.02
3. Restrained planarity
 O201, C201, C202, C203
 with sigma of 0.05
 O4, C1C, C1A, C1B
 with sigma of 0.05
4. Rigid bond restraints
 O4B, C51B, C46B, C47B, C48B, C49B, C50B, C52B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
C36B \\sim C37B \\sim C38B: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C36A \\sim C37A \\sim C38A: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C37B) \\sim Ueq, Uanis(C36B) \\sim Ueq, Uanis(C38B) \\sim Ueq: with sigma
of 0.025 and sigma for terminal atoms of 0.05
6. Rigid body (RIGU) restrains
 O4, C1C, C1A, C1B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O201, C201, C202, C203
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O4A, C46A, C47A, C48A, C49A, C50A, C51A, C52A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C35, C36B, C36A, C37A, C37B, C38B, C38A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
7. Others
 Fixed Sof: O4(0.5) O4B(0.5) O4A(0.5) O201(0.5) C1C(0.5) H1CA(0.5) H1CB(0.5)
 H1CC(0.5) C1A(0.5) C1B(0.5) H1BA(0.5) H1BB(0.5) H1BC(0.5) H35C(0.5) H35D(0.5)
 H35A(0.5) H35B(0.5) C36B(0.5) H36B(0.5) C36A(0.5) H36A(0.5) C37A(0.5)
 H37A(0.5) H37B(0.5) H37C(0.5) C37B(0.5) H37D(0.5) H37E(0.5) H37F(0.5)
 C38B(0.5) H38A(0.5) H38B(0.5) H38C(0.5) C38A(0.5) H38D(0.5) H38E(0.5)
 H38F(0.5) C46A(0.5) C47A(0.5) H47A(0.5) C48A(0.5) H48A(0.5) C49A(0.5)
 C50A(0.5) H50A(0.5) C51A(0.5) H51A(0.5) C51B(0.5) H51B(0.5) C46B(0.5)
 C47B(0.5) H47B(0.5) C48B(0.5) H48B(0.5) C49B(0.5) C50B(0.5) H50B(0.5)
 C52B(0.5) H52A(0.5) H52B(0.5) H52C(0.5) C52A(0.5) H52D(0.5) H52E(0.5)
 H52F(0.5) C201(0.5) C202(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C203(0.5)
 H20D(0.5) H20E(0.5) H20F(0.5)
 Fixed U11: O4(0.15) O201(0.15) C1C(0.15) C1A(0.15) C1B(0.15) C201(0.15)
 C202(0.15) C203(0.15)
 Fixed U12: O4(0) O201(0) C1C(0) C1A(0) C1B(0) C201(0) C202(0) C203(0)
 Fixed U13: O4(0.000004) O201(0.000004) C1C(0.000004) C1A(0.000004)
 C1B(0.000004) C201(0.000004) C202(0.000004) C203(0.000004)
 Fixed U22: O4(0.15) O201(0.15) C1C(0.15) C1A(0.15) C1B(0.15) C201(0.15)
 C202(0.15) C203(0.15)
 Fixed U23: O4(0) O201(0) C1C(0) C1A(0) C1B(0) C201(0) C202(0) C203(0)
 Fixed U33: O4(0.15) O201(0.15) C1C(0.15) C1A(0.15) C1B(0.15) C201(0.15)
 C202(0.15) C203(0.15)
8.a Ternary CH refined with riding coordinates:
 C6(H6), C36B(H36B), C36A(H36A)
8.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C35(H35C,H35D), C35(H35A,H35B)
8.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N31(H31), C10(H10), C11(H11), C13(H13), C14(H14), C17(H17), C18(H18),
 C20(H20), C21(H21), C40(H40), C41(H41), C43(H43), C44(H44), C47A(H47A),
 C48A(H48A), C50A(H50A), C51A(H51A), C51B(H51B), C47B(H47B), C48B(H48B),
 C50B(H50B)
8.d Fitted hexagon refined as free rotating group:
 C51B(C46B,C47B,C48B,C49B,C50B)
8.e Idealised Me refined as rotating group:
 C1C(H1CA,H1CB,H1CC), C1B(H1BA,H1BB,H1BC), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C),
 C15(H15A,H15B,H15C), C22(H22A,H22B,H22C), C37A(H37A,H37B,H37C), C37B(H37D,H37E,
 H37F), C38B(H38A,H38B,H38C), C38A(H38D,H38E,H38F), C45(H45A,H45B,H45C),
 C52B(H52A,H52B,H52C), C52A(H52D,H52E,H52F), C102(H10A,H10B,H10C), C103(H10D,
 H10E,H10F), C202(H20A,H20B,H20C), C203(H20D,H20E,H20F)
;
_shelx_res_checksum              13405
_shelx_hkl_checksum              10640
_shelx_fab_checksum              72195
_ins_header
;
TITL YQ-11-P4_2_scale in P2(1)/n 
REM P2(1)/n (#14 in standard setting)
CELL 1.54184  19.283447  10.840545  24.053284  90.0000  90.2196  90.0000
ZERR    4.00   0.001855   0.000940   0.001335   0.0000   0.0070   0.0000
LATT  1
SYMM -x+1/2, y+1/2,-z+1/2 
SFAC C H N O
UNIT 200.00 240.00 8.00 24.00
TREF
HKLF 4
END
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.872
_oxdiff_exptl_absorpt_empirical_full_min 0.613