Catalyst-Directed Divergent Catalytic Approaches to Expand Structural and Functional Scaffold Diversity via Metallo-Enolcarbene Intermediates
Dong, Kuiyong; Zheng, Haifeng; Su, Yongliang; Humeidi, Ahmad; Arman, Hadi; Xu, Xinfang; Doyle, Michael P.; ACS Catalysis 11 (2021) 4712–4721; doi:10.1021/acscatal.1c01051

data_4518676
_publ_section_title
;
 Catalyst-Directed Divergent Catalytic Approaches to Expand Structural and
 Functional Scaffold Diversity via Metallo-Enolcarbene Intermediates
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              4712
_journal_page_last               4721
_journal_paper_doi               10.1021/acscatal.1c01051
_journal_volume                  11
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H28 F3 N O4 Si'
_chemical_formula_sum            'C22 H28 F3 N O4 Si'
_chemical_formula_weight         455.54
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-12-16
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.10.09 svn.r3662 for Rigaku Oxford Diffraction, GUI svn.r5959)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.38863(8)
_cell_length_b                   11.45356(10)
_cell_length_c                   24.7725(2)
_cell_measurement_reflns_used    10840
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.3960
_cell_measurement_theta_min      3.5630
_cell_volume                     2380.13(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.63a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT n/a (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.967
_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   -123.00 -33.00   0.50    0.06    --  -46.87 -28.00 -52.00  180
  2  \w    -80.00 -15.00   0.50    0.24    --  -88.50  94.00 -92.00  130
  3  \w   -163.00 -73.00   0.50    0.24    --  -88.50 -28.00 -52.00  180
  4  \w     38.00 117.00   0.50    0.24    --  106.69-132.00  86.00  158
  5  \w   -120.00 -83.00   0.50    0.06    --  -46.87 -57.00  60.00   74
  6  \w   -120.00 -87.00   0.50    0.06    --  -46.87-125.00  90.00   66
  7  \w     34.00  96.00   0.50    0.06    --   46.87-125.00   0.00  124
  8  \w    -51.00 -16.00   0.50    0.24    --  -88.50  45.00  90.00   70
  9  \w     34.00  71.00   0.50    0.24    --  106.69 -61.00  60.00   74
 10  \w     34.00  71.00   0.50    0.24    --  106.69 -61.00  90.00   74
 11  \w     34.00  71.00   0.50    0.24    --  106.69 -61.00 -30.00   74
 12  \w     34.00 101.00   0.50    0.24    --  106.69 -77.00 150.00  134
 13  \w     34.00  71.00   0.50    0.24    --  106.69 -61.00-150.00   74
 14  \w   -121.00 -32.00   0.50    0.06    --  -46.87 -37.00 120.00  178
 15  \w   -120.00 -83.00   0.50    0.06    --  -46.87 -57.00  90.00   74
 16  \w   -120.00 -83.00   0.50    0.06    --  -46.87 -57.00-120.00   74
 17  \w   -164.00 -95.00   0.50    0.24    --  -88.50 -15.00 150.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1451807000
_diffrn_orient_matrix_UB_12      -0.0434426000
_diffrn_orient_matrix_UB_13      -0.0324393000
_diffrn_orient_matrix_UB_21      -0.0901016000
_diffrn_orient_matrix_UB_22      -0.0239162000
_diffrn_orient_matrix_UB_23      0.0530507000
_diffrn_orient_matrix_UB_31      -0.0674628000
_diffrn_orient_matrix_UB_32      0.1249770000
_diffrn_orient_matrix_UB_33      -0.0011151000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0386
_diffrn_reflns_av_unetI/netI     0.0325
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            15570
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.687
_diffrn_reflns_theta_min         3.568
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.319
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.557
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.63a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             960
_exptl_crystal_size_max          0.148
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.355
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1704 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(15)
_refine_ls_extinction_coef       0.00052(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.972
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     286
_refine_ls_number_reflns         4571
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.972
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0311
_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^)+(0.0441P)^2^+0.6227P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0780
_refine_ls_wR_factor_ref         0.0797
_reflns_Friedel_coverage         0.668
_reflns_Friedel_fraction_full    0.946
_reflns_Friedel_fraction_max     0.859
_reflns_number_gt                4366
_reflns_number_total             4571
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01051_si_002.cif
_cod_data_source_block           hpd056
_cod_database_code               4518676
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         N1O2F3C25H20
_chemical_oxdiff_usercomment     KD_sample
_shelx_estimated_absorpt_t_max   0.941
_shelx_estimated_absorpt_t_min   0.829
_reflns_odcompleteness_completeness 99.96
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C2(H2A,H2B), C7(H7A,H7B)
2.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C22(H22), C18(H18), C19(H19)
2.c X=CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C16(H16A,H16B,
 H16C), C14(H14A,H14B,H14C)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_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 1.235
_oxdiff_exptl_absorpt_empirical_full_min 0.871