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_1548284
_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         'C23 H27 N O4'
_chemical_formula_sum            'C23 H27 N O4'
_chemical_formula_weight         381.45
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-07-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.0990(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.8292(3)
_cell_length_b                   15.8674(2)
_cell_length_c                   12.3179(2)
_cell_measurement_reflns_used    11720
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.6030
_cell_measurement_theta_min      3.3640
_cell_volume                     4265.80(11)
_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      150.00(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 0.998
_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    -29.00  56.00   1.00    4.00    --   37.04 -38.00  90.00   85
  2  \w     50.00  76.00   1.00    4.00    --   37.04 -99.00 120.00   26
  3  \w     11.00  43.00   1.00    4.00    --   37.04  77.00-120.00   32
  4  \w     35.00  67.00   1.00    4.00    --   37.04  38.00 -30.00   32
  5  \w     26.00  53.00   1.00    4.00    --   37.04  57.00   0.00   27
  6  \w     31.00  95.00   1.00    4.00    --   37.04-133.00 -43.00   64
  7  \w     20.00  58.00   1.00    4.00    --   37.04  38.00 -90.00   38
  8  \w      2.00  36.00   1.00    4.00    --   37.04 -99.00 120.00   34
  9  \w     78.00 103.00   1.00    4.00    --   37.04  77.00   0.00   25
 10  \w    -28.00  54.00   1.00    4.00    --   37.04 -57.00-150.00   82
 11  \w     77.00 105.00   1.00    4.00    --   37.04  38.00 -30.00   28
 12  \w     37.00  91.00   1.00    4.00    --   37.04  57.00-150.00   54
 13  \w     35.00  64.00   1.00    4.00    --   37.04  77.00   0.00   29
 14  \w      0.00  48.00   1.00    4.00    --   37.04 -38.00   0.00   48
 15  \w     58.00 103.00   1.00    4.00    --   37.04  57.00   0.00   45
 16  \w     75.00 106.00   1.00    4.00    --   37.04  38.00 -90.00   31
 17  \w     51.00  96.00   1.00    4.00    --   37.04-136.00 138.00   45
 18  \w     73.00 135.00   1.00   17.00    --  111.00 -25.00   0.00   62
 19  \w     45.00  71.00   1.00   17.00    --  111.00 -25.00   0.00   26
 20  \w     45.00  73.00   1.00   17.00    --  111.00 -25.00-120.00   28
 21  \w     43.00  69.00   1.00   17.00    --  111.00-111.00   0.00   26
 22  \w     63.00 102.00   1.00   17.00    --  111.00 -38.00-180.00   39
 23  \w     49.00 137.00   1.00   17.00    --  111.00 -77.00  60.00   88
 24  \w     91.00 116.00   1.00   17.00    --  111.00-111.00  60.00   25
 25  \w    135.00 163.00   1.00   17.00    --  111.00  50.00-120.00   28
 26  \w     81.00 116.00   1.00   17.00    --  111.00-111.00   0.00   35
 27  \w     43.00 115.00   1.00   17.00    --  111.00 -50.00 150.00   72
 28  \w    113.00 139.00   1.00   17.00    --  111.00 111.00 150.00   26
 29  \w     88.00 124.00   1.00   17.00    --  111.00 -48.00  56.68   36
 30  \w     44.00 125.00   1.00   17.00    --  111.00 -50.00-120.00   81
 31  \w    153.00 178.00   1.00   17.00    --  111.00   0.00 150.00   25
 32  \w     43.00 119.00   1.00   17.00    --  111.00   0.00 150.00   76
 33  \w     87.00 114.00   1.00   17.00    --  111.00 -77.00-180.00   27
 34  \w     94.00 133.00   1.00   17.00    --  111.00  64.00-150.00   39
 35  \w    104.00 145.00   1.00   17.00    --  111.00 -92.00 -60.00   41
 36  \w     73.00 110.00   1.00   17.00    --  111.00-111.00 -60.00   37
 37  \w     43.00  76.00   1.00   17.00    --  111.00-111.00  60.00   33
 38  \w     58.00  84.00   1.00   17.00    --  111.00 -92.00 -60.00   26
 39  \w     45.00 120.00   1.00   17.00    --  111.00 -25.00  90.00   75
 40  \w     66.00 103.00   1.00   17.00    --  111.00-111.00 120.00   37
 41  \w     81.00 106.00   1.00   17.00    --  111.00 -64.00  30.00   25
 42  \w     45.00  70.00   1.00   17.00    --  111.00 -64.00  30.00   25
 43  \w    148.00 177.00   1.00   17.00    --  111.00  64.00-150.00   29
 44  \w     89.00 149.00   1.00   17.00    --  111.00 178.00   0.00   60
 45  \w     47.00  92.00   1.00   17.00    --  111.00 -77.00 120.00   45
 46  \w     99.00 126.00   1.00   17.00    --  111.00 -77.00 120.00   27
 47  \w    123.00 178.00   1.00   17.00    --  111.00  50.00-180.00   55
 48  \w    127.00 152.00   1.00   17.00    --  111.00  12.00   0.00   25
 49  \w     70.00 124.00   1.00   17.00    --  111.00  12.00   0.00   54
 50  \w     87.00 135.00   1.00   17.00    --  111.00 -77.00 -90.00   48
 51  \w     96.00 127.00   1.00   17.00    --  111.00 -25.00-120.00   31
 52  \w     72.00  98.00   1.00   17.00    --  111.00 -66.00 -62.06   26
 53  \w    124.00 156.00   1.00   17.00    --  111.00  50.00 -30.00   32
 54  \w     73.00 112.00   1.00   17.00    --  111.00-111.00-150.00   39
 55  \w     43.00  68.00   1.00   17.00    --  111.00-111.00 150.00   25
 56  \w     91.00 116.00   1.00   17.00    --  111.00-111.00 150.00   25
 57  \w     44.00  70.00   1.00   17.00    --  111.00 -48.00  56.68   26
 58  \w    119.00 144.00   1.00   17.00    --  111.00 178.00  30.00   25
 59  \w     73.00 118.00   1.00   17.00    --  111.00 -30.00 145.35   45
;
_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      0.0695607000
_diffrn_orient_matrix_UB_12      -0.0086673000
_diffrn_orient_matrix_UB_13      0.0203903000
_diffrn_orient_matrix_UB_21      -0.0119027000
_diffrn_orient_matrix_UB_22      -0.0428509000
_diffrn_orient_matrix_UB_23      0.1097956000
_diffrn_orient_matrix_UB_31      -0.0011200000
_diffrn_orient_matrix_UB_32      -0.0866800000
_diffrn_orient_matrix_UB_33      -0.0564144000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            24329
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.814
_diffrn_reflns_theta_min         3.444
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.652
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97039
_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    1.188
_exptl_crystal_description       plate
_exptl_crystal_F_000             1632
_exptl_crystal_size_max          0.214
_exptl_crystal_size_mid          0.121
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.503
_refine_diff_density_min         -0.262
_refine_diff_density_rms         0.038
_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     261
_refine_ls_number_reflns         4309
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0533P)^2^+2.5689P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0953
_refine_ls_wR_factor_ref         0.0987
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3920
_reflns_number_total             4309
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np7b00872_si_002.cif
_cod_data_source_block           YQ-10-P77_scale_compound_12
_cod_depositor_comments
'Adding full bibliography for 1548282--1548286.cif.'
_cod_database_code               1548284
_shelxl_version_number           2014/6
_reflns_odcompleteness_completeness 98.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.a Ternary CH refined with riding coordinates:
 C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C14(H14), C16(H16), C17(H17), C19(H19), C20(H20)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C)
;
_shelx_res_checksum              58041
_shelx_hkl_checksum              19564
_ins_header
;
TITL YQ-10-P77_scale in C2/c 
REM C2/c (#15 in standard setting)
CELL 1.54184  21.829162  15.867400  12.317857  90.0000  91.0986  90.0000
ZERR    8.00   0.000335   0.000226   0.000171   0.0000   0.0014   0.0000
LATT  7
SYMM -x, y,-z+1/2 
SFAC C H N O
UNIT 184.00 216.00 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 1.157
_oxdiff_exptl_absorpt_empirical_full_min 0.804