Synthesis of 3-indolyl all-carbon quaternary centers <i>via</i> Rh/Brønsted acid co-catalyzed three-component reactions of azoalkenes with indoles and diazoacetates.
Yue, Xiao-Jing; Pei, Li-Ping; Wang, Min-Can; Jia, Shi-Kun; Mei, Guang-Jian; Organic & biomolecular chemistry 23 (2025) 5323–5327; doi:10.1039/d5ob00567a

data_7160539
_publ_section_title
;
 Synthesis of 3-indolyl all-carbon quaternary centers <i>via</i>
 Rh/Br&#xf8;nsted acid co-catalyzed three-component reactions of
 azoalkenes with indoles and diazoacetates.
;
_journal_issue                   22
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5323
_journal_page_last               5327
_journal_paper_doi               10.1039/d5ob00567a
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H33 N3 O6'
_chemical_formula_sum            'C32 H33 N3 O6'
_chemical_formula_weight         555.61
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-11-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-10-28 deposited with the CCDC.	2025-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.75449(18)
_cell_length_b                   16.6482(4)
_cell_length_c                   19.5357(4)
_cell_measurement_reflns_used    4831
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.0040
_cell_measurement_theta_min      3.4750
_cell_volume                     2847.26(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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    -59.00  36.00   1.00    2.00    --  -33.50  77.00 150.00   95
  2  \w    -61.00 -36.00   1.00    2.00    --  -33.50 178.00 -30.00   25
  3  \w    -88.00 -39.00   1.00    2.00    --  -33.50 -57.00-150.00   49
  4  \w     73.00 105.00   1.00    2.00    --   36.47-161.00  34.00   32
  5  \w     62.00 104.00   1.00   11.00    --  108.00 -94.00-120.00   42
  6  \w    121.00 168.00   1.00   11.00    --  108.00  77.00 -90.00   47
  7  \w     38.00  88.00   1.00   11.00    --  108.00 -94.00-180.00   50
  8  \w     41.00  88.00   1.00   11.00    --  108.00-111.00  90.00   47
  9  \w     85.00 175.00   1.00   11.00    --  108.00  30.00  90.00   90
 10  \w     93.00 134.00   1.00   11.00    --  108.00 -30.00  90.00   41
 11  \w   -100.00 -60.00   1.00    4.00    --  -33.50 -57.00  90.00   40
 12  \w     65.00 109.00   1.00    4.00    --   36.47 178.00 120.00   44
 13  \w     61.00  86.00   1.00    4.00    --   36.47 178.00 -60.00   25
 14  \w    121.00 173.00   1.00   11.00    --  108.00  77.00 -30.00   52
 15  \w     54.00 119.00   1.00   11.00    --  108.00 -30.00-150.00   65
 16  \w    111.00 137.00   1.00   11.00    --  108.00  77.00-180.00   26
 17  \w    152.00 177.00   1.00   11.00    --  108.00  77.00-180.00   25
 18  \w     89.00 121.00   1.00   11.00    --  108.00 -77.00-150.00   32
 19  \w     44.00  70.00   1.00   11.00    --  108.00 -77.00-150.00   26
 20  \w   -100.00 -51.00   1.00    4.00    --  -33.50 -57.00  90.00   49
 21  \w     80.00 105.00   1.00    4.00    --   36.47  57.00-150.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0097041000
_diffrn_orient_matrix_UB_12      0.0703408000
_diffrn_orient_matrix_UB_13      0.0511000000
_diffrn_orient_matrix_UB_21      -0.0403271000
_diffrn_orient_matrix_UB_22      -0.0575771000
_diffrn_orient_matrix_UB_23      0.0590071000
_diffrn_orient_matrix_UB_31      0.1709732000
_diffrn_orient_matrix_UB_32      -0.0175543000
_diffrn_orient_matrix_UB_33      0.0110736000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0387
_diffrn_reflns_av_unetI/netI     0.0528
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            11643
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.539
_diffrn_reflns_theta_min         3.488
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.736
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72980
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
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    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             1176
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.363
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1584 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         5327
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0601
_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^)+(0.0895P)^2^+0.5206P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1603
_refine_ls_wR_factor_ref         0.1723
_reflns_Friedel_coverage         0.744
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                4576
_reflns_number_total             5327
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00567a2.cif
_cod_data_source_block           202311315
_cod_depositor_comments
'Adding full bibliography for 7160539--7160540.cif.'
_cod_original_cell_volume        2847.27(11)
_cod_database_code               7160539
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.891
_reflns_odcompleteness_completeness 99.93
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C28, C29
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C11(H11)
4.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C26(H26A,H26B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C8(H8), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C28(H28), C32(H32), C31(H31), C30(H30), C29(H29)
4.d Fitted hexagon refined as free rotating group:
 C28(C27,C32,C31,C30,C29)
4.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              6672
_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 1.455
_oxdiff_exptl_absorpt_empirical_full_min 0.838