Tandem [4+1+1] Annulation Approach to 4-Acyl-3,4-dihydropyrrolo[1,2- a]pyrazines: Diastereoselective Construction of Dihydropyrazine Units from Pyrroles.
Dagar, Anuradha; Bae, Gi Hun; Lee, Jeong Hwa; Kim, Ikyon; The Journal of organic chemistry 84 (2019) 6916–6927; doi:10.1021/acs.joc.9b00724

data_4034598
_publ_section_title
;
 Tandem [4+1+1] Annulation Approach to 4-Acyl-3,4-dihydropyrrolo[1,2-
 a]pyrazines: Diastereoselective Construction of Dihydropyrazine Units
 from Pyrroles.
;
_journal_issue                   11
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6916
_journal_page_last               6927
_journal_paper_doi               10.1021/acs.joc.9b00724
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C20 H15 Cl N2 O'
_chemical_formula_sum            'C20 H15 Cl N2 O'
_chemical_formula_weight         334.79
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   19.0715(7)
_cell_length_b                   19.0715(7)
_cell_length_c                   18.6402(11)
_cell_measurement_reflns_used    3800
_cell_measurement_temperature    291.9(2)
_cell_measurement_theta_max      22.6290
_cell_measurement_theta_min      2.6200
_cell_volume                     6779.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      291.9(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2262
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.912
_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    -51.00 -11.00   1.00    7.67    --  -11.04 107.00 113.00   40
  2  \w    -13.00  19.00   1.00    7.67    --  -11.04-107.00  14.00   32
  3  \w     -5.00  50.00   1.00    7.67    --   11.51-107.00  14.00   55
  4  \w     -7.00  23.00   1.00    7.67    --  -11.04 -99.00-150.00   30
  5  \w    -20.00   9.00   1.00    7.67    --  -11.04 -99.00-180.00   29
  6  \w    -20.00   6.00   1.00    7.67    --  -11.04 -99.00  60.00   26
  7  \w     35.00  85.00   1.00    7.67    --   11.51 178.00 -90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0158073000
_diffrn_orient_matrix_UB_12      0.0278023000
_diffrn_orient_matrix_UB_13      -0.0194155000
_diffrn_orient_matrix_UB_21      0.0324332000
_diffrn_orient_matrix_UB_22      -0.0182144000
_diffrn_orient_matrix_UB_23      0.0003498000
_diffrn_orient_matrix_UB_31      -0.0090415000
_diffrn_orient_matrix_UB_32      -0.0166995000
_diffrn_orient_matrix_UB_33      -0.0327133000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0587
_diffrn_reflns_av_unetI/netI     0.0588
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.912
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            23818
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.912
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.585
_diffrn_reflns_theta_min         2.136
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.233
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57126
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light white'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_description       cube
_exptl_crystal_F_000             2784
_exptl_crystal_size_max          0.391
_exptl_crystal_size_mid          0.267
_exptl_crystal_size_min          0.143
_refine_diff_density_max         0.143
_refine_diff_density_min         -0.277
_refine_diff_density_rms         0.035
_refine_ls_extinction_coef       0.00031(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         4339
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.1342
_refine_ls_R_factor_gt           0.0642
_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^)+(0.0340P)^2^+4.7139P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1104
_refine_ls_wR_factor_ref         0.1343
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2405
_reflns_number_total             4339
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00724_si_002.cif
_cod_data_source_block           exp_1330
_cod_original_cell_volume        6779.9(6)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4034598
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C21 H14 Cl N O'
_chemical_oxdiff_usercomment     IK-4APP
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.914
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C003(H003), C007(H007)
2.b Aromatic/amide H refined with riding coordinates:
 C005(H005), C010(H010), C011(H011), C014(H014), C016(H016), C017(H017),
 C018(H018), C019(H019), C020(H020), C021(H021), C022(H022), C023(H023),
 C024(H024)
;
_olex2_date_sample_data_collection 2018-11-12
_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 1.424
_oxdiff_exptl_absorpt_empirical_full_min 0.600