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_7160540
_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_formula_moiety         'C29 H35 N3 O6, 2(C H Cl3)'
_chemical_formula_sum            'C31 H37 Cl6 N3 O6'
_chemical_formula_weight         760.33
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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                113.796(5)
_cell_angle_beta                 90.707(4)
_cell_angle_gamma                110.206(4)
_cell_formula_units_Z            2
_cell_length_a                   12.7618(5)
_cell_length_b                   13.0621(6)
_cell_length_c                   13.4282(7)
_cell_measurement_reflns_used    8617
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.2730
_cell_measurement_theta_min      3.9840
_cell_volume                     1891.85(19)
_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    'ShelXT (Sheldrick, 2015)'
_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 0.988
_diffrn_measured_fraction_theta_max 0.988
_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    -31.00  16.00   1.00    1.00    --    0.00 -57.00 -90.00   47
  2  \w    -63.00 -36.00   1.00    1.00    --    0.00 -57.00 -90.00   27
  3  \w    -17.00  19.00   1.00    1.00    --    0.00 -77.00-180.00   36
  4  \w   -102.00 -62.00   1.00    2.25    --  -33.50 -57.00  60.00   40
  5  \w    -58.00 -23.00   1.00    2.25    --  -33.50 -57.00  60.00   35
  6  \w    -56.00  36.00   1.00    2.25    --  -33.50  37.00  60.00   92
  7  \w     65.00  99.00   1.00    2.25    --   36.47 178.00  60.00   34
  8  \w     10.00  37.00   1.00    2.25    --   36.47 -99.00 150.00   27
  9  \w     25.00  84.00   1.00    2.25    --   36.47-125.00  46.00   59
 10  \w     -1.00  24.00   1.00    2.25    --   36.47  93.00 -42.33   25
 11  \w     44.00  72.00   1.00    2.25    --   36.47 -99.00 150.00   28
 12  \w     61.00 108.00   1.00    2.25    --   36.47 178.00-180.00   47
 13  \w     61.00 110.00   1.00    2.25    --   36.47 178.00   0.00   49
 14  \w     -1.00  24.00   1.00    2.25    --   36.47  94.00  46.67   25
 15  \w     62.00 103.00   1.00    2.25    --   36.47 178.00 -90.00   41
 16  \w     -1.00  24.00   1.00    2.25    --   36.47  93.00 156.42   25
 17  \w      9.00  34.00   1.00    2.25    --   44.00  89.00-111.83   25
 18  \w      9.00  34.00   1.00    2.25    --   44.00  88.00 120.38   25
 19  \w     16.00  42.00   1.00    2.25    --   48.00  84.00-152.84   26
 20  \w     16.00  41.00   1.00    2.25    --   48.00  83.00 114.50   25
 21  \w     17.00  42.00   1.00    2.25    --   48.00  81.00 -79.73   25
 22  \w     17.00  42.00   1.00    2.25    --   48.00  82.00  41.67   25
 23  \w     16.00  41.00   1.00    2.25    --   48.00  84.00 -32.04   25
 24  \w     17.00  42.00   1.00    2.25    --   48.00  81.00 172.72   25
 25  \w     30.00  58.00   1.00    2.25    --   52.00  73.00  16.35   28
 26  \w     83.00 124.00   1.00    2.25    --   56.00  73.00 -30.24   41
 27  \w     32.00  80.00   1.00    2.25    --   56.00  69.00 104.31   48
 28  \w     68.00  94.00   1.00    2.25    --   56.00  73.00 157.18   26
 29  \w     31.00  64.00   1.00    2.25    --   56.00  71.00 -81.73   33
 30  \w     37.00  63.00   1.00    2.25    --   56.00  69.00  48.34   26
 31  \w     30.00  58.00   1.00    2.25    --   56.00  73.00 157.18   28
 32  \w     96.00 122.00   1.00    2.25    --   56.00  71.00 -81.73   26
 33  \w     30.00  68.00   1.00    2.25    --   56.00  73.00 -30.24   38
 34  \w     93.00 124.00   1.00    2.25    --   56.00  69.00 104.31   31
 35  \w     32.00  88.00   1.00    2.25    --   56.00  72.00-167.50   56
 36  \w     98.00 126.00   1.00    2.25    --   60.00  67.00  72.53   28
 37  \w     39.00  79.00   1.00    2.25    --   60.00  67.00  72.53   40
 38  \w     41.00 120.00   1.00    2.25    --   60.00  55.00 -96.20   79
 39  \w    124.00 158.00   1.00   11.00    --   88.00  39.00  -6.85   34
 40  \w     66.00  92.00   1.00   11.00    --   88.00  39.00  -6.85   26
 41  \w     89.00 115.00   1.00   11.00    --  108.00  61.00   0.00   26
 42  \w     88.00 122.00   1.00   11.00    --  108.00  45.00 150.00   34
 43  \w     41.00  73.00   1.00   11.00    --  108.00 -94.00-120.00   32
 44  \w     78.00 109.00   1.00   11.00    --  108.00-111.00-180.00   31
 45  \w    127.00 176.00   1.00   11.00    --  108.00  61.00  30.00   49
 46  \w     88.00 120.00   1.00   11.00    --  108.00  45.00-150.00   32
 47  \w     89.00 119.00   1.00   11.00    --  108.00  45.00  60.00   30
 48  \w     44.00 109.00   1.00   11.00    --  108.00-111.00   0.00   65
 49  \w     88.00 158.00   1.00   11.00    --  108.00  45.00 -60.00   70
 50  \w     88.00 167.00   1.00   11.00    --  108.00  61.00 150.00   79
 51  \w     88.00 123.00   1.00   11.00    --  108.00  45.00 120.00   35
 52  \w    151.00 176.00   1.00   11.00    --  108.00  61.00-180.00   25
 53  \w     88.00 113.00   1.00   11.00    --  108.00  61.00-180.00   25
 54  \w     88.00 114.00   1.00   11.00    --  108.00  61.00  30.00   26
 55  \w     88.00 174.00   1.00   11.00    --  108.00  61.00 -30.00   86
 56  \w     88.00 114.00   1.00   11.00    --  108.00  45.00   0.00   26
 57  \w    130.00 175.00   1.00   11.00    --  108.00  61.00-150.00   45
 58  \w     88.00 125.00   1.00   11.00    --  108.00  61.00-150.00   37
 59  \w     88.00 120.00   1.00   11.00    --  108.00  61.00 -90.00   32
 60  \w    135.00 174.00   1.00   11.00    --  108.00  61.00 -90.00   39
 61  \w     48.00  93.00   1.00   11.00    --  108.00 -94.00  90.00   45
 62  \w    127.00 172.00   1.00   11.00    --  108.00  61.00   0.00   45
 63  \w     42.00 109.00   1.00   11.00    --  108.00-111.00  90.00   67
 64  \w    130.00 169.00   1.00   11.00    --  108.00  61.00  60.00   39
 65  \w     89.00 126.00   1.00   11.00    --  108.00  61.00  60.00   37
 66  \w     88.00 117.00   1.00   11.00    --  108.00  45.00  30.00   29
 67  \w    133.00 176.00   1.00   11.00    --  108.00  61.00 120.00   43
 68  \w     45.00 109.00   1.00   11.00    --  108.00-111.00 -90.00   64
 69  \w     88.00 129.00   1.00   11.00    --  108.00  61.00 120.00   41
 70  \w    137.00 176.00   1.00   11.00    --  108.00  45.00-180.00   39
 71  \w    134.00 175.00   1.00   11.00    --  108.00  61.00  90.00   41
 72  \w     89.00 118.00   1.00   11.00    --  108.00  45.00 -90.00   29
 73  \w     88.00 118.00   1.00   11.00    --  108.00  61.00  90.00   30
 74  \w     88.00 176.00   1.00   11.00    --  108.00  61.00 -60.00   88
 75  \w     40.00 125.00   1.00   11.00    --  108.00 -61.00  90.00   85
 76  \w     88.00 117.00   1.00   11.00    --  108.00  45.00  90.00   29
 77  \w     88.00 114.00   1.00   11.00    --  108.00  45.00-120.00   26
 78  \w     88.00 114.00   1.00   11.00    --  108.00  45.00-180.00   26
 79  \w    129.00 175.00   1.00   11.00    --  108.00  61.00-120.00   46
 80  \w     88.00 114.00   1.00   11.00    --  108.00  61.00-120.00   26
 81  \w     38.00  48.00   1.00   11.00    --  108.00 -94.00 -60.00   10
;
_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      0.1002218000
_diffrn_orient_matrix_UB_12      0.1020007000
_diffrn_orient_matrix_UB_13      -0.0085075000
_diffrn_orient_matrix_UB_21      -0.0360892000
_diffrn_orient_matrix_UB_22      -0.0619478000
_diffrn_orient_matrix_UB_23      -0.1266882000
_diffrn_orient_matrix_UB_31      -0.0757142000
_diffrn_orient_matrix_UB_32      0.0723095000
_diffrn_orient_matrix_UB_33      0.0102798000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0403
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            26449
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.655
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.503
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71177
_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    1.335
_exptl_crystal_description       block
_exptl_crystal_F_000             788
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.454
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     446
_refine_ls_number_reflns         6667
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0884
_refine_ls_R_factor_gt           0.0728
_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^)+(0.1173P)^2^+1.1042P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2098
_refine_ls_wR_factor_ref         0.2288
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5111
_reflns_number_total             6667
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00567a2.cif
_cod_data_source_block           202311316
_cod_depositor_comments
'Adding full bibliography for 7160539--7160540.cif.'
_cod_original_cell_volume        1891.85(17)
_cod_database_code               7160540
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4
_shelx_estimated_absorpt_t_max   0.662
_shelx_estimated_absorpt_t_min   0.515
_reflns_odcompleteness_completeness 98.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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. Restrained distances
 Cl1-Cl2
 2.9 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Cl4) = Uanis(Cl4A)
Uanis(Cl5A) = Uanis(Cl5)
Uanis(Cl6) = Uanis(Cl6A)
Uanis(Cl2A) = Uanis(Cl1A)
Uanis(Cl1) = Uanis(Cl2)
Uanis(Cl3A) = Uanis(Cl3)
4. Others
 Sof(Cl4A)=Sof(Cl5)=Sof(Cl6A)=Sof(H31A)=1-FVAR(1)
 Sof(Cl4)=Sof(Cl5A)=Sof(Cl6)=Sof(H31)=FVAR(1)
 Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=Sof(H30A)=1-FVAR(2)
 Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(H30)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C30(H30), C30(H30A), C31(H31A), C31(H31)
5.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3A), C4(H4), C8(H8), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17)
5.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C19(H19A,H19B,H19C), C22(H22A,H22B,H22C), C24(H24A,H24B,
 H24C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              26838
_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 2.600
_oxdiff_exptl_absorpt_empirical_full_min 0.757