Synthesis of Tryptophan-containing 2,5-Diketopiperazines via Sequential C‒H Activation: Total Syntheses of Tryprostatin A, Maremycins A and B
Yin, Xue-Song; Qi, Wei-Yi; Shi, Bing-Feng; Chemical Science  (2021) –; doi:10.1039/D1SC02343H

data_1564596
_publ_section_title
;
 Synthesis of Tryptophan-containing 2,5-Diketopiperazines via Sequential
 C--H Activation: Total Syntheses of Tryprostatin A, Maremycins A and B
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02343H
_journal_year                    2021
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C35 H25 N5 O7 S'
_chemical_formula_sum            'C35 H25 N5 O7 S'
_chemical_formula_weight         659.66
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-01-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5289)
;
_audit_update_record
;
2021-01-15 deposited with the CCDC.	2021-09-07 downloaded from the CCDC.
;
_cell_angle_alpha                90.0
_cell_angle_beta                 101.966(4)
_cell_angle_gamma                90.0
_cell_formula_units_Z            4
_cell_length_a                   10.5548(4)
_cell_length_b                   27.6947(9)
_cell_length_c                   10.8041(4)
_cell_measurement_reflns_used    7943
_cell_measurement_temperature    170.0
_cell_measurement_theta_max      67.3109
_cell_measurement_theta_min      3.1888
_cell_volume                     3089.5(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      170.0
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_details
;
  1 omega   30.00   91.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.4438   38.0000    0.0000 61

  2 omega    7.00   90.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.4438 -114.0000  133.0000 83

  3 omega   15.00  115.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.4438   77.0000 -120.0000 100

  4 omega   -8.00   25.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       40.4438  -38.0000  -60.0000 33

  5 omega -125.00  -99.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -83.0000  132.0000   29.0000 26

  6 omega   79.00  171.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  111.0000   30.0000 92

  7 omega   93.00  168.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000  120.0000 75

  8 omega    9.00  117.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -91.0000   11.0000 108

  9 omega   80.00  168.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000 -120.0000 88

 10 omega   71.00  111.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000  120.0000 40

 11 omega   19.00   77.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -45.0000  120.0000 58

 12 omega   79.00  168.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000   45.0000  -30.0000 89

 13 omega   15.00   46.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000  120.0000 31

 14 omega   18.00   85.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000   30.0000 67

 15 omega   88.00  124.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -77.0000   30.0000 36

 16 omega    9.00  122.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       93.5000  -92.0000 -121.0000 113
;
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0029899000
_diffrn_orient_matrix_UB_12      0.0547939000
_diffrn_orient_matrix_UB_13      -0.0237380000
_diffrn_orient_matrix_UB_21      -0.1490024000
_diffrn_orient_matrix_UB_22      0.0014752000
_diffrn_orient_matrix_UB_23      -0.0258758000
_diffrn_orient_matrix_UB_31      0.0050908000
_diffrn_orient_matrix_UB_32      0.0094528000
_diffrn_orient_matrix_UB_33      0.1415513000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0983
_diffrn_reflns_av_unetI/netI     0.0734
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            21562
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.425
_diffrn_reflns_theta_max         67.425
_diffrn_reflns_theta_min         3.191
_diffrn_source                   'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.440
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38477
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
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    1.418
_exptl_crystal_description       block
_exptl_crystal_F_000             1368
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.46
_exptl_crystal_size_min          0.4
_refine_diff_density_max         0.393
_refine_diff_density_min         -0.733
_refine_diff_density_rms         0.092
_refine_ls_abs_structure_details
;
 Flack x determined using 3747 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     867
_refine_ls_number_reflns         10748
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0765
_refine_ls_R_factor_gt           0.0692
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1142P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1685
_refine_ls_wR_factor_ref         0.1795
_reflns_Friedel_coverage         0.910
_reflns_Friedel_fraction_full    0.942
_reflns_Friedel_fraction_max     0.942
_reflns_number_gt                9415
_reflns_number_total             10748
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc02343h2.cif
_cod_data_source_block           170111_d_189_4
_cod_original_cell_volume        3089.5(3)
_cod_database_code               1564596
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'c10 h10 n2 o8 s1'
_cell_oxdiff_angle_alpha         90.006(4)
_cell_oxdiff_angle_beta          101.956(5)
_cell_oxdiff_angle_gamma         89.946(5)
_cell_oxdiff_length_a            10.5601(7)
_cell_oxdiff_length_b            27.6966(14)
_cell_oxdiff_length_c            10.7975(4)
_cell_oxdiff_measurement_reflns_used 7943
_cell_oxdiff_volume              3089.5(3)
_shelx_estimated_absorpt_t_max   0.597
_shelx_estimated_absorpt_t_min   0.545
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(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:
 C11(H11), C12(H12), C46(H46), C47(H47)
2.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C1(H1), C2(H2A), C3(H3), C7(H7), C8(H8), C9(H9), C14(H14), C17(H17),
 C18(H18), C19(H19), C20(H20), C25(H25), C26(H26), C27(H27), C28(H28), C31(H31),
  C32(H32), C34(H34), C35(H35), N7(H7A), C36(H36), C37(H37), C38(H38), C42(H42),
  C43(H43), C44(H44), C49(H49), C52(H52), C53(H53), C54(H54), C55(H55),
 C60(H60), C61(H61), C62(H62), C63(H63), C66(H66), C67(H67), C69(H69), C70(H70)
2.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C64(H64A,H64B,H64C)
;
_shelx_res_checksum              37629
_shelx_hkl_checksum              41877
_olex2_submission_special_instructions 'No special instructions were received'