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_1548285
_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         'C22 H25 N O4'
_chemical_formula_sum            'C22 H25 N O4'
_chemical_formula_weight         367.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5375)
;
_cell_angle_alpha                90
_cell_angle_beta                 98.1460(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.43710(10)
_cell_length_b                   14.48440(10)
_cell_length_c                   22.3921(2)
_cell_measurement_reflns_used    21597
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      73.6840
_cell_measurement_theta_min      3.5700
_cell_volume                     3993.10(6)
_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)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -30.00  54.00   1.00    2.50    --   36.95 -57.00-150.00   84
  2  \w      1.00  76.00   1.00    2.50    --   36.95 -99.00-180.00   75
  3  \w     20.00 104.00   1.00    2.50    --   36.95  57.00  30.00   84
  4  \w      8.00 108.00   1.00    2.50    --   36.95  19.00 150.00  100
  5  \w     10.00 105.00   1.00    2.50    --   36.95  77.00 -30.00   95
  6  \w     23.00  90.00   1.00    2.50    --   36.95-125.00 120.00   67
  7  \w     94.00 178.00   1.00   15.00    --  111.00  50.00 -30.00   84
  8  \w     91.00 178.00   1.00   15.00    --  111.00  64.00  60.00   87
  9  \w     91.00 178.00   1.00   15.00    --  111.00  64.00   0.00   87
 10  \w     41.00 116.00   1.00   15.00    --  111.00-111.00 120.00   75
 11  \w     91.00 178.00   1.00   15.00    --  111.00  64.00 -60.00   87
 12  \w     84.00 178.00   1.00   15.00    --  111.00  77.00  30.00   94
 13  \w     43.00 128.00   1.00   15.00    --  111.00 -50.00 -90.00   85
 14  \w     92.00 178.00   1.00   15.00    --  111.00  38.00  90.00   86
 15  \w    100.00 178.00   1.00   15.00    --  111.00 111.00-120.00   78
 16  \w     41.00 116.00   1.00   15.00    --  111.00-111.00 -90.00   75
 17  \w     41.00 116.00   1.00   15.00    --  111.00-111.00-120.00   75
 18  \w     42.00 146.00   1.00   15.00    --  111.00 -92.00 -60.00  104
 19  \w     41.00 116.00   1.00   15.00    --  111.00-111.00-150.00   75
 20  \w    100.00 178.00   1.00   15.00    --  111.00 111.00 -90.00   78
 21  \w    -30.00  54.00   1.00    2.50    --   36.95 -57.00 -30.00   84
 22  \w     18.00 106.00   1.00    2.50    --   36.95  38.00-120.00   88
 23  \w     10.00 105.00   1.00    2.50    --   36.95  77.00 120.00   95
 24  \w    -32.00  56.00   1.00    2.50    --   36.95 -38.00  60.00   88
 25  \w     23.00  90.00   1.00    2.50    --   36.95-125.00   0.00   67
 26  \w     18.00 106.00   1.00    2.50    --   36.95  38.00 -60.00   88
 27  \w     65.00 165.00   1.00   15.00    --  111.00  12.00-120.00  100
;
_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      0.1186189000
_diffrn_orient_matrix_UB_12      -0.0115063000
_diffrn_orient_matrix_UB_13      -0.0112846000
_diffrn_orient_matrix_UB_21      0.0038319000
_diffrn_orient_matrix_UB_22      -0.0962556000
_diffrn_orient_matrix_UB_23      0.0295568000
_diffrn_orient_matrix_UB_31      -0.0395061000
_diffrn_orient_matrix_UB_32      -0.0438422000
_diffrn_orient_matrix_UB_33      -0.0618705000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0226
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            41605
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.795
_diffrn_reflns_theta_min         3.590
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.678
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96687
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             1568
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.069
_refine_diff_density_max         0.440
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     556
_refine_ls_number_reflns         8040
_refine_ls_number_restraints     147
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0386
_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^)+(0.0486P)^2^+1.4933P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1005
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7086
_reflns_number_total             8040
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np7b00872_si_002.cif
_cod_data_source_block           YQ-11-P11-2_scale_compound_13
_cod_depositor_comments
'Adding full bibliography for 1548282--1548286.cif.'
_cod_database_code               1548285
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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. Uiso/Uaniso restraints and constraints
O34B \\sim C46B \\sim C47B \\sim C48B \\sim C49B \\sim C50B \\sim C51B \\sim
C52B: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
O34A \\sim C46A \\sim C47A \\sim C48A \\sim C49A \\sim C50A \\sim C51A \\sim
C52A: within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
3. Rigid body (RIGU) restrains
 O34B, C46B, C47B, C48B, C49B, C50B, C51B, C52B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Others
 Fixed Sof: O34A(0.6) O34B(0.4) C47B(0.4) H47B(0.4) C46B(0.4) C51B(0.4)
 H51B(0.4) C50B(0.4) H50B(0.4) C49B(0.4) C48B(0.4) H48B(0.4) C51A(0.6)
 H51A(0.6) C46A(0.6) C47A(0.6) H47A(0.6) C48A(0.6) H48A(0.6) C49A(0.6)
 C50A(0.6) H50A(0.6) C52B(0.4) H52A(0.4) H52B(0.4) H52C(0.4) C52A(0.6)
 H52D(0.6) H52E(0.6) H52F(0.6)
5.a Ternary CH refined with riding coordinates:
 C36(H36), C6(H6)
5.b Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C5(H5A,H5B)
5.c Aromatic/amide H refined with riding coordinates:
 C40(H40), C41(H41), C43(H43), C44(H44), C47B(H47B), C51B(H51B), C50B(H50B),
 C48B(H48B), C51A(H51A), C47A(H47A), C48A(H48A), C50A(H50A), C10(H10), C11(H11),
  C13(H13), C14(H14), C17(H17), C18(H18), C20(H20), C21(H21)
5.d Fitted hexagon refined as free rotating group:
 C47B(C46B,C51B,C50B,C49B,C48B), C51A(C46A,C47A,C48A,C49A,C50A)
5.e Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C45(H45A,H45B,H45C), C52B(H52A,H52B,
 H52C), C52A(H52D,H52E,H52F), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C15(H15A,H15B,
 H15C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              42805
_shelx_hkl_checksum              78942
_ins_header
;
TITL YQ-11-P11-2_scale in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 1.54184  12.437082  14.484403  22.392098  90.0000  98.1458  90.0000
ZERR    8.00   0.000092   0.000110   0.000170   0.0000   0.0007   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H N O
UNIT 176.00 216.00 8.00 32.00
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 1.116
_oxdiff_exptl_absorpt_empirical_full_min 0.886