Brønsted acid-promoted synthesis of highly functionalized tetrahydrocarbazoles from diethyl (<i>E</i>)-5-diazo-4-oxohex-2-enedioate.
Arunkumar, Vemula; Balamurugan, Rengarajan; Organic & biomolecular chemistry 22 (2024) 9214–9218; doi:10.1039/d4ob00992d

data_7160128
_publ_section_title
;
 Br&#xf8;nsted acid-promoted synthesis of highly functionalized
 tetrahydrocarbazoles from diethyl
 (<i>E</i>)-5-diazo-4-oxohex-2-enedioate.
;
_journal_issue                   47
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9214
_journal_page_last               9218
_journal_paper_doi               10.1039/d4ob00992d
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C15 H14 N O3'
_chemical_formula_sum            'C15 H14 N O3'
_chemical_formula_weight         256.27
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-11
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.12.18 svn.r3554 for Rigaku Oxford Diffraction, GUI svn.r1)
;
_audit_update_record
;
2023-06-26 deposited with the CCDC.	2024-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                81.898(3)
_cell_angle_beta                 73.226(3)
_cell_angle_gamma                73.495(4)
_cell_formula_units_Z            2
_cell_length_a                   8.6191(4)
_cell_length_b                   8.8839(4)
_cell_length_c                   9.3999(3)
_cell_measurement_reflns_used    5392
_cell_measurement_temperature    296
_cell_measurement_theta_max      23.2030
_cell_measurement_theta_min      2.2630
_cell_volume                     659.38(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (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
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.970
_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    -11.00  86.00   0.50    2.00    --   16.22  61.00 -30.00  194
  2  \w     -7.00  58.00   0.50    2.00    --   16.22-104.00-115.00  130
  3  \w     10.00  71.00   0.50    2.00    --   16.22-125.00-180.00  122
  4  \w    -37.00  21.00   0.50    2.00    --  -15.60 -94.00-180.00  116
  5  \w    -41.00  58.00   0.50    2.00    --  -15.60  30.00 -90.00  198
  6  \w     -8.00  86.00   0.50    2.00    --   16.22  45.00-180.00  188
  7  \w    -43.00  54.00   0.50    2.00    --  -15.60  61.00-180.00  194
  8  \w    -37.00  21.00   0.50    2.00    --  -15.60 -94.00 -60.00  116
  9  \w    -54.00  41.00   0.50    2.00    --   16.22 -45.00 -30.00  190
 10  \w    -53.00  44.00   0.50    2.00    --   16.22 -61.00  30.00  194
 11  \w    -37.00  21.00   0.50    2.00    --  -15.60 -94.00 120.00  116
 12  \w    -57.00  41.00   0.50    2.00    --   16.22 -30.00  60.00  196
 13  \w    -10.00  90.00   0.50    2.00    --   16.22  30.00 120.00  200
 14  \w    -42.00 -14.00   0.50    2.00    --   16.22 133.00  39.16   56
 15  \w    -57.00   7.00   0.50    2.00    --  -15.60 104.00 -14.00  128
 16  \w    -57.00  41.00   0.50    2.00    --   16.22 -30.00 -90.00  196
 17  \w    -70.00 -10.00   0.50    2.00    --  -15.60 125.00-120.00  120
 18  \w    -89.00   9.00   0.50    2.00    --  -15.60 -30.00-150.00  196
 19  \w    -88.00  16.00   0.50    2.00    --  -15.60 -77.00-150.00  208
 20  \w    -88.00  16.00   0.50    2.00    --  -15.60 -77.00   0.00  208
 21  \w    -85.00  -4.00   0.50    2.00    --  -15.60 -61.00  30.00  162
 22  \w    -70.00 -10.00   0.50    2.00    --  -15.60 125.00   0.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0039147000
_diffrn_orient_matrix_UB_12      0.0774981000
_diffrn_orient_matrix_UB_13      -0.0327811000
_diffrn_orient_matrix_UB_21      -0.0536696000
_diffrn_orient_matrix_UB_22      0.0309248000
_diffrn_orient_matrix_UB_23      0.0678486000
_diffrn_orient_matrix_UB_31      0.0708052000
_diffrn_orient_matrix_UB_32      0.0008103000
_diffrn_orient_matrix_UB_33      0.0236414000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0607
_diffrn_reflns_av_unetI/netI     0.0401
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            15968
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         2.268
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66435
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic yellowish yellow'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       plate
_exptl_crystal_F_000             270
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.399
_refine_diff_density_min         -0.302
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     184
_refine_ls_number_reflns         2817
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1099
_refine_ls_R_factor_gt           0.0664
_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^)+(0.1084P)^2^+0.1229P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1824
_refine_ls_wR_factor_ref         0.2301
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1563
_reflns_number_total             2817
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00992d2.cif
_cod_data_source_block           rb47
_cod_depositor_comments
'Adding full bibliography for 7160128--7160130.cif.'
_cod_database_code               7160128
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O '
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.982
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Others
 Fixed Sof: H13(0.5) H13A(0.5) C14B(0.5) H14A(0.5) H14B(0.5) H14C(0.5)
 C14A(0.5) H14D(0.5) H14E(0.5) H14F(0.5)
3.a Ternary CH refined with riding coordinates:
 C3(H3)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
3.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C8(H8), C10(H10), C9(H9), C13(H13), C13(H13A)
3.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C14B(H14A,H14B,H14C), C14A(H14D,H14E,H14F)
;
_shelx_res_checksum              96939
_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 1.869
_oxdiff_exptl_absorpt_empirical_full_min 0.468