Highly enantioselective Rh-catalyzed asymmetric reductive dearomatization of multi-nitrogen polycyclic pyrazolo[1,5-<i>a</i>]pyrimidines.
Xie, Chaochao; Xiao, Guiying; Guo, Qianling; Wu, Xiaoxue; Zi, Guofu; Ding, Wanjian; Hou, Guohua; Chemical science 14 (2023) 9048–9054; doi:10.1039/d3sc02086j

data_1569589
_publ_section_title
;
 Highly enantioselective Rh-catalyzed asymmetric reductive dearomatization
 of multi-nitrogen polycyclic pyrazolo[1,5-<i>a</i>]pyrimidines.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              9048
_journal_page_last               9054
_journal_paper_doi               10.1039/d3sc02086j
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C19 H20 N3 O'
_chemical_formula_sum            'C19 H20 N3 O'
_chemical_formula_weight         306.38
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-06-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-02-21 deposited with the CCDC.	2023-07-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.34260(10)
_cell_length_b                   12.1336(2)
_cell_length_c                   20.3228(2)
_cell_measurement_reflns_used    7933
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      76.2240
_cell_measurement_theta_min      4.2400
_cell_volume                     1564.01(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.974
_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     10.00  68.00   0.50    0.05    --   46.91 -74.00 129.00  116
  2  \w     36.00  61.00   0.50    0.05    --  104.75 -77.00  90.00   50
  3  \w     70.00 100.00   0.50    0.05    --  104.75 -77.00  90.00   60
  4  \w     39.00  69.00   0.50    0.05    --  104.75 -61.00 150.00   60
  5  \w     40.00 118.00   0.50    0.05    --   46.91  47.00  71.00  156
  6  \w     76.00 149.00   0.50    0.05    --  104.75 125.00  90.00  146
  7  \w   -157.00-123.00   0.50    0.05    -- -102.00 -15.00 150.00   68
  8  \w   -114.00 -86.00   0.50    0.05    --  -46.91-125.00 -30.00   56
  9  \w   -112.00 -72.00   0.50    0.05    --  -46.91-125.00 -90.00   80
 10  \w   -173.00 -89.00   0.50    0.05    -- -102.00 -45.00-120.00  168
 11  \w   -142.00 -94.00   0.50    0.05    -- -102.00 -47.00 -77.00   96
 12  \w    -63.00 -32.00   0.50    0.05    -- -102.00  61.00 150.00   62
 13  \w    -57.00 -30.00   0.50    0.05    -- -102.00  74.00-102.00   54
 14  \w    -69.00 -39.00   0.50    0.05    -- -102.00  61.00-150.00   60
 15  \w    -68.00 -33.00   0.50    0.05    -- -102.00  61.00-180.00   70
 16  \w    -66.00 -31.00   0.50    0.05    -- -102.00  61.00   0.00   70
 17  \w     32.00 105.00   0.50    0.05    --  104.75-118.00  54.00  146
 18  \w     66.00 109.00   0.50    0.05    --  104.75 -94.00 -60.00   86
;
_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      -0.1422868000
_diffrn_orient_matrix_UB_12      0.0168940000
_diffrn_orient_matrix_UB_13      0.0606175000
_diffrn_orient_matrix_UB_21      0.0078727000
_diffrn_orient_matrix_UB_22      -0.1246623000
_diffrn_orient_matrix_UB_23      0.0141758000
_diffrn_orient_matrix_UB_31      0.1966688000
_diffrn_orient_matrix_UB_32      0.0171425000
_diffrn_orient_matrix_UB_33      0.0432680000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0275
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            8762
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.988
_diffrn_reflns_theta_min         4.244
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.651
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58223
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
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    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             652
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.265
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 1222 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.06(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3124
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0351
_refine_ls_R_factor_gt           0.0343
_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^)+(0.0529P)^2^+0.3120P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0889
_refine_ls_wR_factor_ref         0.0894
_reflns_Friedel_coverage         0.692
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.939
_reflns_number_gt                3044
_reflns_number_total             3124
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02086j2.cif
_cod_data_source_block           20220608d_auto
_cod_depositor_comments          'Adding full bibliography for 1569589.cif.'
_cod_database_code               1569589
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         N1O1C1H1
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.909
_diffrn_oxdiff_digest_frames
;
0124e006863e34c5965a5aba5b0dad77dd016048b6b
;
_diffrn_oxdiff_digest_hkl
;
0191f0365c2835e34be73a37a1a17d89afa569
;
_reflns_odcompleteness_completeness 99.82
_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 Ternary CH refined with riding coordinates:
 C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3), C2(H2), C8(H8), C9(H9), C10(H10), C11(H11), C15(H15),
 C16(H16), C17(H17), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
;
_shelx_res_checksum              97028
_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 1.588
_oxdiff_exptl_absorpt_empirical_full_min 0.581