Regiodivergent synthesis of pyrazino-indolines <i>vs.</i> triazocines <i>via</i> α-imino carbenes addition to imidazolidines.
Guarnieri-Ibáñez, Alejandro; de Aguirre, Adiran; Besnard, Céline; Poblador-Bahamonde, Amalia I; Lacour, Jérôme; Chemical science 12 (2020) 1479–1485; doi:10.1039/d0sc05725h

data_1559637
_publ_section_title
;
 Regiodivergent synthesis of pyrazino-indolines <i>vs.</i> triazocines
 <i>via</i> \a-imino carbenes addition to imidazolidines.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              1479
_journal_page_last               1485
_journal_paper_doi               10.1039/d0sc05725h
_journal_volume                  12
_journal_year                    2020
_chemical_formula_moiety         'C32 H33 N3 O2 S'
_chemical_formula_sum            'C32 H33 N3 O2 S'
_chemical_formula_weight         523.67
_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             2017-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2020-07-09 deposited with the CCDC.	2020-11-23 downloaded from the CCDC.
;
_cell_angle_alpha                111.225(3)
_cell_angle_beta                 98.183(3)
_cell_angle_gamma                98.485(3)
_cell_formula_units_Z            4
_cell_length_a                   10.9678(3)
_cell_length_b                   15.3212(4)
_cell_length_c                   17.9064(5)
_cell_measurement_reflns_used    16273
_cell_measurement_temperature    180.01(10)
_cell_measurement_theta_max      73.7010
_cell_measurement_theta_min      3.1300
_cell_volume                     2710.92(15)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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      N~2~
_diffrn_ambient_temperature      180.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.983
_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     19.00  44.00   1.00    1.00    --   56.00  80.00 -18.88   25
  2  \w     32.00  63.00   1.00    1.00    --   68.00  77.00 -24.54   31
  3  \w     82.00 124.00   1.00    1.00    --   68.00  77.00 -24.54   42
  4  \w    108.00 154.00   1.00    1.00    --   72.00  76.00 -73.52   46
  5  \w    118.00 173.00   1.00    4.00    --  110.40 111.00-150.00   55
  6  \w    110.00 152.00   1.00    4.00    --  110.40  77.00 -90.00   42
  7  \w    109.00 175.00   1.00    4.00    --  110.40 111.00   0.00   66
  8  \w    115.00 178.00   1.00    4.00    --  110.40  77.00 120.00   63
  9  \w    113.00 150.00   1.00    4.00    --  110.40  77.00  60.00   37
 10  \w    108.00 149.00   1.00    1.00    --   68.00  76.00 169.68   41
 11  \w     77.00 108.00   1.00    4.00    --  110.40  61.00  90.00   31
 12  \w     78.00 126.00   1.00    4.00    --  110.40  61.00 150.00   48
 13  \w     79.00 106.00   1.00    4.00    --  110.40  61.00 120.00   27
 14  \w     74.00 100.00   1.00    4.00    --  110.40  77.00  60.00   26
 15  \w     74.00 177.00   1.00    4.00    --  110.40  77.00  30.00  103
 16  \w     80.00 107.00   1.00    4.00    --  110.40  61.00 -60.00   27
 17  \w     74.00 177.00   1.00    4.00    --  110.40  77.00 -30.00  103
 18  \w     78.00 103.00   1.00    4.00    --  110.40  61.00-180.00   25
 19  \w     74.00 176.00   1.00    4.00    --  110.40  77.00-120.00  102
 20  \w     77.00 104.00   1.00    4.00    --  110.40  61.00   0.00   27
 21  \w     78.00 118.00   1.00    4.00    --  110.40  61.00 -30.00   40
 22  \w     74.00 100.00   1.00    4.00    --  110.40  77.00 -60.00   26
 23  \w     74.00 100.00   1.00    4.00    --  110.40  77.00 -90.00   26
 24  \w     74.00 139.00   1.00    4.00    --  110.40  77.00-150.00   65
 25  \w     74.00 177.00   1.00    4.00    --  110.40  77.00-180.00  103
 26  \w     74.00 132.00   1.00    4.00    --  110.40  77.00   0.00   58
 27  \w     74.00 101.00   1.00    4.00    --  110.40  77.00 120.00   27
 28  \w     74.00 178.00   1.00    4.00    --  110.40  77.00  90.00  104
 29  \w     74.00 150.00   1.00    4.00    --  110.40  77.00 150.00   76
 30  \w     55.00 123.00   1.00    1.00    --   38.94  77.00 150.00   68
 31  \w     33.00  62.00   1.00    1.00    --   68.00  76.00 169.68   29
 32  \w     36.00  80.00   1.00    1.00    --   72.00  77.00 109.24   44
 33  \w     36.00  74.00   1.00    1.00    --   72.00  77.00  70.73   38
 34  \w     32.00  60.00   1.00    1.00    --   68.00  76.00  31.92   28
 35  \w     19.00  44.00   1.00    1.00    --   56.00  80.00  72.06   25
 36  \w     19.00  44.00   1.00    1.00    --   56.00  82.00  19.32   25
 37  \w     36.00  67.00   1.00    1.00    --   72.00  76.00 -73.52   31
 38  \w     28.00  54.00   1.00    1.00    --   64.00  77.00 -92.81   26
 39  \w     36.00 140.00   1.00    1.00    --   72.00  77.00-147.44  104
 40  \w     60.00 146.00   1.00    4.00    --  110.40 178.00-120.00   86
 41  \w     19.00  44.00   1.00    1.00    --   56.00  81.00-152.46   25
 42  \w      6.00  34.00   1.00    1.00    --   44.00  87.00-105.05   28
 43  \w     -4.00  21.00   1.00    1.00    --   38.94  96.00  19.65   25
 44  \w      4.00  49.00   1.00    1.00    --   38.94  77.00 150.00   45
 45  \w     19.00  45.00   1.00    1.00    --   56.00  80.00 168.20   26
 46  \w    -59.00  -8.00   1.00    1.00    --  -38.94 -57.00 150.00   51
 47  \w    -94.00 -16.00   1.00    1.00    --  -38.94 -38.00  30.00   78
 48  \w    -71.00  39.00   1.00    1.00    --  -38.94  57.00 -90.00  110
 49  \w     35.00 115.00   1.00    4.00    --  110.40-111.00-150.00   80
 50  \w     55.00 130.00   1.00    1.00    --   38.94-178.00-150.00   75
 51  \w     31.00 108.00   1.00    4.00    --  110.40 -94.00 -60.00   77
 52  \w     38.00 113.00   1.00    4.00    --  110.40-111.00  60.00   75
 53  \w   -117.00 -74.00   1.00    1.00    --  -38.94 -57.00 150.00   43
 54  \w   -117.00  -7.00   1.00    1.00    --  -38.94 -57.00 -60.00  110
 55  \w   -129.00 -57.00   1.00    1.00    --  -38.94 178.00-150.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0899192000
_diffrn_orient_matrix_UB_12      -0.0312750000
_diffrn_orient_matrix_UB_13      0.0549050000
_diffrn_orient_matrix_UB_21      -0.0248423000
_diffrn_orient_matrix_UB_22      -0.1003657000
_diffrn_orient_matrix_UB_23      -0.0691347000
_diffrn_orient_matrix_UB_31      0.1114378000
_diffrn_orient_matrix_UB_32      0.0339461000
_diffrn_orient_matrix_UB_33      -0.0335616000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            42868
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.705
_diffrn_reflns_theta_min         3.169
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.327
_exptl_absorpt_correction_T_max  0.942
_exptl_absorpt_correction_T_min  0.719
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       plate
_exptl_crystal_F_000             1112
_exptl_crystal_size_max          0.411
_exptl_crystal_size_mid          0.182
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.244
_refine_diff_density_min         -0.419
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     698
_refine_ls_number_reflns         10776
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0381
_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^)+(0.0555P)^2^+0.5227P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0989
_refine_ls_wR_factor_ref         0.1064
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8967
_reflns_number_total             10776
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc05725h2.cif
_cod_data_source_block           ajgi-665-23
_cod_depositor_comments
;Adding full bibliography for 1559635--1559639.cif.

 Adding full bibliography for 1559635--1559639.cif.
;
_cod_original_cell_volume        2710.90(15)
_cod_database_code               1559637
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C32 H33 N3 O2 S1'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.29
_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:
 C5(H5), C5B(H5B)
2.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C24(H24A,H24B), C14B(H14C,H14D), C15B(H15C,
 H15D), C24B(H24C,H24D)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C10(H10), C11(H11), C18(H18), C19(H19), C22(H22), C23(H23), C27(H27),
 C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C37(H37), C38(H38),
  C7B(H7B), C10B(H10B), C11B(H11B), C18B(H18B), C19B(H19B), C22B(H22B),
 C23B(H23B), C27B(H27B), C28B(H28B), C29B(H29B), C30B(H30B), C31B(H31B),
 C33B(H33B), C34B(H34B), C37B(H37B), C38B(H38B)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C21(H21A,H21B,H21C), C36(H36A,H36B,H36C), C9B(H9BA,H9BB,
 H9BC), C21B(H21D,H21E,H21F), C36B(H36D,H36E,H36F)
;
_shelx_res_checksum              34469
_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 1.338
_oxdiff_exptl_absorpt_empirical_full_min 0.695