Regio- and Stereoselective Synthesis of the Core Structure of Hexahydrobenzo[<i>c</i>]phenanthridine Alkaloids via Redox-Neutral Cp*Rh(III)-Catalyzed C-H/N-H Annulation of Cyclic Alkenes with Benzamides.
Das Adhikari, Gopal Krushna; Chebolu, Rajesh; Ravikumar, Ponneri Chandrababu; ACS omega 5 (2020) 24033–24044; doi:10.1021/acsomega.0c03434

data_4518035
_publ_section_title
;
 Regio- and Stereoselective Synthesis of the Core Structure of
 Hexahydrobenzo[<i>c</i>]phenanthridine Alkaloids via Redox-Neutral
 Cp*Rh(III)-Catalyzed C-H/N-H Annulation of Cyclic Alkenes with
 Benzamides.
;
_journal_issue                   37
_journal_name_full               'ACS omega'
_journal_page_first              24033
_journal_page_last               24044
_journal_paper_doi               10.1021/acsomega.0c03434
_journal_volume                  5
_journal_year                    2020
_chemical_formula_moiety         'C19 H19 N O'
_chemical_formula_sum            'C19 H19 N O'
_chemical_formula_weight         277.35
_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             2019-09-16
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                73.971(3)
_cell_angle_beta                 81.252(4)
_cell_angle_gamma                86.515(3)
_cell_formula_units_Z            2
_cell_length_a                   9.1117(4)
_cell_length_b                   9.1126(3)
_cell_length_c                   9.5279(4)
_cell_measurement_reflns_used    6901
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      30.9950
_cell_measurement_theta_min      3.7800
_cell_volume                     751.36(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.807
_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    -13.00  45.00   0.50   45.67    --    5.13-106.00 117.00  116
  2  \w    -13.00  34.00   0.50   45.67    --   -5.59-106.00 117.00   94
  3  \w    -61.00   9.00   0.50   45.67    --    5.13 -38.00   0.00  140
  4  \w    -61.00   9.00   0.50   45.67    --    5.13 -38.00 120.00  140
  5  \w    -20.00  41.00   0.50   45.67    --    5.13 -99.00 -60.00  122
  6  \w    -61.00   1.00   0.50   45.67    --    5.13 -38.00-180.00  124
  7  \w    -61.00   9.00   0.50   45.67    --    5.13 -38.00-120.00  140
  8  \w     13.00  57.00   0.50   45.67    --    5.13  57.00-180.00   88
  9  \w    -19.00   7.00   0.50   45.67    --   -5.59 -99.00  30.00   52
 10  \w    -20.00   5.00   0.50   45.67    --   -5.59 -99.00  90.00   50
 11  \w    -18.00  17.00   0.50   45.67    --   -5.59 -99.00-150.00   70
 12  \w    -20.00   9.00   0.50   45.67    --   -5.59 -99.00 -60.00   58
 13  \w    -19.00   6.00   0.50   45.67    --   -5.59 -99.00 -90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0335293000
_diffrn_orient_matrix_UB_12      -0.0084449000
_diffrn_orient_matrix_UB_13      0.0739475000
_diffrn_orient_matrix_UB_21      -0.0667062000
_diffrn_orient_matrix_UB_22      -0.0229625000
_diffrn_orient_matrix_UB_23      -0.0169219000
_diffrn_orient_matrix_UB_31      0.0251378000
_diffrn_orient_matrix_UB_32      -0.0772180000
_diffrn_orient_matrix_UB_33      0.0191464000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0455
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.807
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            14692
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.807
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.009
_diffrn_reflns_theta_min         3.277
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.075
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65905
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
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    1.226
_exptl_crystal_description       cube
_exptl_crystal_F_000             296
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.424
_refine_diff_density_min         -0.212
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         3872
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.111
_refine_ls_R_factor_all          0.0855
_refine_ls_R_factor_gt           0.0650
_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^)+(0.1230P)^2^+0.0540P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1924
_refine_ls_wR_factor_ref         0.2076
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2810
_reflns_number_total             3872
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao0c03434_si_003.cif
_cod_data_source_block           pcr-gkd-ipr
_cod_depositor_comments
;
Adding full bibliography for 4518035--4518036.cif.

2025-09-12
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C38 H38 N2 O2'
_cod_original_formula_weight         554.70
_cod_original_formula_moiety         '2(C19 H19 N O)'
_cod_original_formula_units_Z            1
_cod_database_code               4518035
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C38 H38 N2 O2 '
_diffrn_oxdiff_ac3_digest_frames
;
013b89e44bf9c195308d4043b3aebdb53e000253284
;
_diffrn_oxdiff_ac3_digest_hkl
;
01033de693f4ee09ddeb4d1f74ab579f6d785a
;
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_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:
 C008(H008), C00C(H00C), C00I(H00I)
2.b Secondary CH2 refined with riding coordinates:
 C00F(H00A,H00F)
2.c Aromatic/amide H refined with riding coordinates:
 N002(H002), C009(H009), C00B(H00B), C00D(H00D), C00E(H00E), C00G(H00G),
 C00H(H00H), C00J(H00J)
2.d Idealised Me refined as rotating group:
 C00K(H00K,H00L,H00M), C00L(H00N,H00O,H00P)
;
_shelx_res_checksum              81384
_shelx_hkl_checksum              7362
_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 1.405
_oxdiff_exptl_absorpt_empirical_full_min 0.585