A Rh-catalyzed three-component reaction for the diastereoselective synthesis of pyrazolone derivatives with contiguous quaternary stereocenters.
Ao, Chaoqun; Huang, Jingjing; Xu, Xinfang; Jia, Shikun; Kang, Zhenghui; Hu, Wenhao; Organic & biomolecular chemistry 18 (2020) 3466–3470; doi:10.1039/d0ob00482k

data_7157463
_publ_section_title
;
 A Rh-catalyzed three-component reaction for the diastereoselective
 synthesis of pyrazolone derivatives with contiguous quaternary
 stereocenters.
;
_journal_issue                   18
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3466
_journal_page_last               3470
_journal_paper_doi               10.1039/d0ob00482k
_journal_volume                  18
_journal_year                    2020
_chemical_formula_moiety         'C31 H32 Br N3 O6'
_chemical_formula_sum            'C31 H32 Br N3 O6'
_chemical_formula_weight         622.50
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-11-16 deposited with the CCDC.	2020-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.2080(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.39580(10)
_cell_length_b                   10.3211(2)
_cell_length_c                   33.5425(5)
_cell_measurement_reflns_used    13423
_cell_measurement_temperature    100
_cell_measurement_theta_max      75.5820
_cell_measurement_theta_min      4.4850
_cell_volume                     2905.94(8)
_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_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.945
_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 -24.00   0.50    0.05    --  -46.50 150.00 136.00  172
  2  \w   -119.00 -54.00   0.50    0.05    --  -46.50-150.00  91.00  130
  3  \w    -94.00  -9.00   0.50    0.05    --  -46.50 122.00 -25.00  170
  4  \w   -119.00 -73.00   0.50    0.05    --  -46.50-122.00-106.00   92
  5  \w     13.00  94.00   0.50    0.05    --   46.50-122.00-106.00  162
  6  \w   -114.00 -27.00   0.50    0.20    -- -100.00 122.00 -25.00  174
  7  \w   -171.00 -58.00   0.50    0.20    -- -100.00-150.00  91.00  226
  8  \w   -103.00 -45.00   0.50    0.20    -- -100.00 150.00 136.00  116
  9  \w   -172.00 -74.00   0.50    0.20    -- -100.00-122.00-106.00  196
 10  \w     74.00 103.00   0.50    0.20    --  107.00-122.00-106.00   58
 11  \w     90.00 115.00   0.50    0.20    --  107.00 150.00 136.00   50
 12  \w   -115.00 -73.00   0.50    0.05    --  -46.50-125.00   0.00   84
 13  \w   -119.00 -24.00   0.50    0.05    --  -46.50 -77.00-120.00  190
 14  \w     45.00 115.00   0.50    0.05    --   46.50  38.00 -90.00  140
 15  \w    -77.00 -28.00   0.50    0.20    -- -100.00  61.00-180.00   98
 16  \w   -172.00 -82.00   0.50    0.20    -- -100.00 -94.00   0.00  180
 17  \w   -116.00 -91.00   0.50    0.20    -- -100.00  61.00-180.00   50
 18  \w   -159.00 -77.00   0.50    0.20    -- -100.00 -77.00-180.00  164
 19  \w     35.00 107.00   0.50    0.20    --  107.00 -94.00  90.00  144
 20  \w    140.00 178.00   0.50    0.20    --  107.00  30.00 -30.00   76
 21  \w     35.00 109.00   0.50    0.20    --  107.00 -94.00 -90.00  148
 22  \w     95.00 136.00   0.50    0.20    --  107.00  30.00 -30.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0466904000
_diffrn_orient_matrix_UB_12      -0.0597237000
_diffrn_orient_matrix_UB_13      0.0406711000
_diffrn_orient_matrix_UB_21      0.0394280000
_diffrn_orient_matrix_UB_22      0.1360581000
_diffrn_orient_matrix_UB_23      0.0163703000
_diffrn_orient_matrix_UB_31      -0.1731078000
_diffrn_orient_matrix_UB_32      0.0149149000
_diffrn_orient_matrix_UB_33      0.0136119000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0488
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            27965
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.990
_diffrn_reflns_theta_min         2.635
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.333
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59215
_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    1.423
_exptl_crystal_description       block
_exptl_crystal_F_000             1288
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.891
_refine_diff_density_min         -1.019
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     375
_refine_ls_number_reflns         5797
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0704
_refine_ls_R_factor_gt           0.0647
_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^)+(0.0324P)^2^+15.6780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1481
_refine_ls_wR_factor_ref         0.1546
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5194
_reflns_number_total             5797
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob00482k2.cif
_cod_data_source_block           caiju_082_181115_2
_cod_depositor_comments          'Adding full bibliography for 7157463.cif.'
_cod_database_code               7157463
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.800
_shelx_estimated_absorpt_t_min   0.541
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 Secondary CH2 refined with riding coordinates:
 C00W(H00D,H00F)
2.b Aromatic/amide H refined with riding coordinates:
 N009(H009), C00E(H00E), C00K(H00K), C00M(H00M), C00N(H00N), C00P(H00P),
 C00Q(H00Q), C00R(H00R), C00S(H00S), C00U(H00U), C00X(H00X), C00Y(H00Y),
 C00Z(H00Z), C011(H011), C013(H013)
2.c Idealised Me refined as rotating group:
 C00T(H00A,H00B,H00C), C010(H01A,H01B,H01C), C012(H01D,H01E,H01F), C014(H01G,
 H01H,H01I), C015(H01J,H01K,H01L)
;
_shelx_res_checksum              76407
_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 1.483
_oxdiff_exptl_absorpt_empirical_full_min 0.647