A highly diastereoselective one-pot Ugi/radical spirocyclization/aza-Michael addition sequence.
Khan, Salman; Chatterjee, Abhradeep; Nair, Akshay M.; Volla, Chandra M. R.; Organic & biomolecular chemistry 22 (2024) 3887–3892; doi:10.1039/d4ob00610k

data_7159909
_publ_section_title
;
 A highly diastereoselective one-pot Ugi/radical
 spirocyclization/aza-Michael addition sequence.
;
_journal_issue                   19
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3887
_journal_page_last               3892
_journal_paper_doi               10.1039/d4ob00610k
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C29 H21 Br N2 O3 S, C2 H6 O S'
_chemical_formula_sum            'C31 H27 Br N2 O4 S2'
_chemical_formula_weight         635.57
_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             2020-02-26
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2023-10-02 deposited with the CCDC.	2024-04-22 downloaded from the CCDC.
;
_cell_angle_alpha                87.085(2)
_cell_angle_beta                 81.887(2)
_cell_angle_gamma                82.628(2)
_cell_formula_units_Z            8
_cell_length_a                   13.7999(4)
_cell_length_b                   15.4016(4)
_cell_length_c                   27.5518(8)
_cell_measurement_reflns_used    32120
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.3780
_cell_measurement_theta_min      2.0460
_cell_volume                     5746.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (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      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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   -110.00  19.00   1.00    8.00    --  -20.00 -72.00 -36.00  129
  2  \w    -94.00  19.00   1.00    8.00    --  -20.00 -72.00-180.00  113
  3  \w    -35.00  70.00   1.00    8.00    --  -20.00   0.00 108.00  105
  4  \w    -35.00  19.00   1.00    8.00    --  -20.00 -72.00  36.00   54
  5  \w    -39.00  -9.00   1.00    8.00    --  -20.00 -72.00-108.00   30
  6  \w    -53.00 -23.00   1.00    8.00    --  -20.00 -72.00 108.00   30
  7  \w    -59.00  70.00   1.00    8.00    --  -20.00  72.00-108.00  129
  8  \w    -59.00  31.00   1.00    8.00    --  -20.00  72.00  36.00   90
  9  \w    -59.00  31.00   1.00    8.00    --  -20.00  72.00-180.00   90
 10  \w    -56.00  30.00   1.00    8.00    --  -20.00  72.00 -36.00   86
 11  \w    -59.00  -6.00   1.00    8.00    --  -20.00  72.00 108.00   53
 12  \w    -39.00  -8.00   1.00    8.00    --  -20.00   0.00-180.00   31
 13  \w   -110.00 -42.00   1.00    8.00    --  -20.00   0.00 -36.00   68
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0451490000
_diffrn_orient_matrix_UB_12      -0.0176140000
_diffrn_orient_matrix_UB_13      0.0082091000
_diffrn_orient_matrix_UB_21      -0.0110996000
_diffrn_orient_matrix_UB_22      0.0271694000
_diffrn_orient_matrix_UB_23      0.0205756000
_diffrn_orient_matrix_UB_31      -0.0239788000
_diffrn_orient_matrix_UB_32      -0.0333228000
_diffrn_orient_matrix_UB_33      0.0136470000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0958
_diffrn_reflns_av_unetI/netI     0.0742
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            110921
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.502
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.616
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65858
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (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    1.469
_exptl_crystal_description       block
_exptl_crystal_F_000             2608
_exptl_crystal_size_max          0.201
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.062
_refine_diff_density_max         3.648
_refine_diff_density_min         -2.229
_refine_diff_density_rms         0.152
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1449
_refine_ls_number_reflns         20237
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.1215
_refine_ls_R_factor_gt           0.0811
_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^)+(0.1487P)^2^+9.5240P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2120
_refine_ls_wR_factor_ref         0.2553
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13424
_reflns_number_total             20237
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00610k2.cif
_cod_data_source_block           cmrv-sk-969_mo
_cod_depositor_comments
;
          Adding full bibliography for 7159909.cif.

2024-12-16
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C124 H108 Br4 N8 O16 S8'
_cod_original_formula_weight         2542.30
_cod_original_formula_moiety         '4(C29 H21 Br N2 O3 S), 4(C2 H6 O S)'
_cod_original_formula_units_Z            2
_cod_database_code               7159909
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.737
_reflns_odcompleteness_completeness 92.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.12
_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. Uiso/Uaniso restraints and constraints
Uanis(O5) \\sim Ueq, Uanis(S1) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.001
3.a Ternary CH refined with riding coordinates:
 C010(H010), C013(H013), C017(H017), C01D(H01D), C01K(H01K), C01U(H01U),
 C025(H025), C02K(H02K)
3.b Secondary CH2 refined with riding coordinates:
 C01N(H01A,H01B), C01T(H01C,H01E), C022(H02C,H02D), C02D(H02A,H02B)
3.c Aromatic/amide H refined with riding coordinates:
 N00L(H00L), N00M(H00M), N00N(H00N), N00Q(H00Q), C01G(H01G), C01O(H01O),
 C01P(H01P), C01S(H01S), C01X(H01X), C01Y(H01Y), C01Z(H01Z), C020(H020),
 C024(H024), C026(H026), C028(H028), C029(H029), C02C(H02E), C02E(H02G),
 C02F(H02F), C02I(H02I), C02L(H02L), C02N(H02N), C02P(H02P), C02Q(H02Q),
 C02R(H02R), C02T(H02T), C02U(H02U), C02V(H02V), C02W(H02W), C02Y(H02Y),
 C02Z(H02Z), C030(H030), C031(H031), C032(H032), C036(H036), C038(H038),
 C039(H039), C03A(H03A), C03C(H03C), C03D(H03D), C03E(H03E), C03G(H03G),
 C03H(H03H), C03I(H03I), C03K(H03K), C03L(H03L), C03M(H03M), C03N(H03N),
 C03O(H03O), C03P(H03P), C03Q(H03Q), C03R(H03R), C03S(H03S), C03T(H03T),
 C03U(H03U), C03V(H03V), C03W(H03W), C03X(H03X), C03Y(H03Y), C03Z(H03Z),
 C040(H040), C041(H041), C042(H042), C043(H043), C044(H044), C045(H045),
 C046(H046), C047(H047)
3.d Idealised Me refined as rotating group:
 C048(H04A,H04B,H04C), C049(H04G,H04H,H04I), C04A(H04J,H04K,H04L), C04B(H04D,
 H04E,H04F), C04C(H04M,H04N,H04O), C04F(H04P,H04Q,H04R), C2(H2A,H2B,H2C),
 C3(H3A,H3B,H3C)
;
_shelx_res_checksum              81662
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.513
_oxdiff_exptl_absorpt_empirical_full_min 0.713