Formal nucleophilic pyrrolylmethylation via palladium-based auto-tandem catalysis: switchable regiodivergent synthesis and remote chirality transfer
Chen, Zhi; Li, Yu-Fan; Tan, Shun-Zhong; Ouyang, Qin; Chen, Zhi-Chao; Du, Wei; Chen, Ying-Chun; Chemical Science 13 (2022) 12433–12439; doi:10.1039/D2SC05210E

data_1567732
_publ_section_title
;
 Formal nucleophilic pyrrolylmethylation via palladium-based auto-tandem
 catalysis: switchable regiodivergent synthesis and remote chirality
 transfer
;
_journal_issue                   42
_journal_name_full               'Chemical Science'
_journal_page_first              12433
_journal_page_last               12439
_journal_paper_doi               10.1039/D2SC05210E
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C27 H28 N2 O4 S2'
_chemical_formula_sum            'C27 H28 N2 O4 S2'
_chemical_formula_weight         508.63
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-11-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2022-07-07 deposited with the CCDC.	2022-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.065(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4288(3)
_cell_length_b                   10.4362(3)
_cell_length_c                   26.2815(7)
_cell_measurement_reflns_used    4396
_cell_measurement_temperature    296.87(12)
_cell_measurement_theta_max      71.2160
_cell_measurement_theta_min      4.5520
_cell_volume                     2571.65(13)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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      296.87(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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    -57.00  36.00   1.00    1.20    --  -34.98  38.00  60.00   93
  2  \w    -53.00  33.00   1.00    1.20    --  -34.98  57.00 -90.00   86
  3  \w    -34.00  64.00   1.00    1.20    --   34.98 -77.00 -60.00   98
  4  \w      1.00  75.00   1.00    1.20    --   34.98 -99.00-120.00   74
  5  \w     16.00 103.00   1.00    1.20    --   34.98  57.00   0.00   87
  6  \w    -34.00  64.00   1.00    1.20    --   34.98 -77.00 -30.00   98
  7  \w    -33.00  53.00   1.00    1.20    --   34.98 -57.00-150.00   86
  8  \w     87.00 177.00   1.00    4.79    --  106.90  45.00   0.00   90
  9  \w     57.00 151.00   1.00    4.79    --  106.90 178.00-180.00   94
 10  \w     82.00 174.00   1.00    4.79    --  106.90 145.00-106.00   92
 11  \w     87.00 177.00   1.00    4.79    --  106.90  45.00  60.00   90
 12  \w     39.00 127.00   1.00    4.79    --  106.90 -61.00  90.00   88
 13  \w     37.00 110.00   1.00    4.79    --  106.90 -94.00 120.00   73
 14  \w     35.00 133.00   1.00    4.79    --  106.90 -30.00-120.00   98
 15  \w     39.00 127.00   1.00    4.79    --  106.90 -61.00 -30.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1102698000
_diffrn_orient_matrix_UB_12      -0.0004283000
_diffrn_orient_matrix_UB_13      0.0392873000
_diffrn_orient_matrix_UB_21      0.1212625000
_diffrn_orient_matrix_UB_22      0.0140992000
_diffrn_orient_matrix_UB_23      0.0437536000
_diffrn_orient_matrix_UB_31      -0.0119579000
_diffrn_orient_matrix_UB_32      0.1469215000
_diffrn_orient_matrix_UB_33      -0.0040605000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0507
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            14349
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.330
_diffrn_reflns_theta_min         3.382
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.169
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30661
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_description       plate
_exptl_crystal_F_000             1072
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.455
_refine_diff_density_min         -0.295
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     319
_refine_ls_number_reflns         4931
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0639
_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^)+(0.1235P)^2^+0.4727P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1703
_refine_ls_wR_factor_ref         0.1898
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3991
_reflns_number_total             4931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05210e2.cif
_cod_data_source_block           4a
_cod_depositor_comments
'Adding full bibliography for 1567732--1567733.cif.'
_cod_original_cell_volume        2571.67(13)
_cod_database_code               1567732
_reflns_odcompleteness_completeness 99.90
_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.a Ternary CH refined with riding coordinates:
 C00C(H00C)
2.b Secondary CH2 refined with riding coordinates:
 C00G(H00A,H00B)
2.c Aromatic/amide H refined with riding coordinates:
 N007(H007), C00E(H00E), C00F(H00F), C00I(H00I), C00J(H00J), C00K(H00K),
 C00M(H00M), C00N(H00N), C00O(H00O), C00Q(H00Q), C00R(H00R), C00S(H00S),
 C00T(H00T), C00U(H00U), C00V(H00V), C00W(H00W)
2.d Idealised Me refined as rotating group:
 C00X(H00D,H00G,H00H), C00Y(H00L,H00P,H00X), C00Z(H00Y,H,HA)
;
_shelx_res_checksum              25108
_shelx_hkl_checksum              2031
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2020-11-10
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.494
_oxdiff_exptl_absorpt_empirical_full_min 0.673