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_4518677
_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         'C26 H38 Br N O4 Si'
_chemical_formula_sum            'C26 H38 Br N O4 Si'
_chemical_formula_weight         536.57
_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             2020-07-22
_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            8
_cell_length_a                   11.36280(10)
_cell_length_b                   14.94170(10)
_cell_length_c                   32.8659(3)
_cell_measurement_reflns_used    37426
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      76.3100
_cell_measurement_theta_min      2.6900
_cell_volume                     5579.96(8)
_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      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 1.000
_diffrn_measured_fraction_theta_max 0.982
_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     66.00 120.00   0.50    0.05    --   46.87 171.00-170.00  108
  2  \w    -80.00 -15.00   0.50    0.20    --  -88.50  95.00 -36.00  130
  3  \w   -163.00 -73.00   0.50    0.20    --  -88.50 -31.00  35.00  180
  4  \w    105.00 178.00   0.50    0.20    --  106.69  95.00 -36.00  146
  5  \w    102.00 178.00   0.50    0.20    --  106.69 114.00  47.00  152
  6  \w   -120.00 -87.00   0.50    0.05    --  -46.87-125.00-180.00   66
  7  \w   -120.00 -87.00   0.50    0.05    --  -46.87-125.00 150.00   66
  8  \w    -30.00  29.00   0.50    0.05    --  -46.87  19.00 -90.00  118
  9  \w   -120.00 -83.00   0.50    0.05    --  -46.87 -57.00-150.00   74
 10  \w   -120.00 -87.00   0.50    0.05    --  -46.87-125.00   0.00   66
 11  \w    -30.00  29.00   0.50    0.05    --  -46.87  19.00   0.00  118
 12  \w     34.00  96.00   0.50    0.05    --   46.87-125.00  60.00  124
 13  \w    -51.00 -16.00   0.50    0.20    --  -88.50  45.00 -30.00   70
 14  \w    -51.00 -16.00   0.50    0.20    --  -88.50  45.00-180.00   70
 15  \w     95.00 178.00   0.50    0.20    --  106.69 125.00  30.00  166
 16  \w     34.00  71.00   0.50    0.20    --  106.69 -61.00   0.00   74
 17  \w     34.00 101.00   0.50    0.20    --  106.69 -77.00-150.00  134
 18  \w     34.00  71.00   0.50    0.20    --  106.69 -61.00 -60.00   74
 19  \w     34.00 101.00   0.50    0.20    --  106.69 -77.00 -90.00  134
 20  \w     91.00 178.00   0.50    0.20    --  106.69  30.00 -60.00  174
 21  \w     34.00 105.00   0.50    0.20    --  106.69 -94.00  90.00  142
 22  \w     34.00 101.00   0.50    0.20    --  106.69 -77.00 120.00  134
 23  \w     34.00  71.00   0.50    0.20    --  106.69 -61.00 120.00   74
 24  \w     34.00  71.00   0.50    0.20    --  106.69 -61.00  30.00   74
 25  \w   -121.00 -32.00   0.50    0.05    --  -46.87 -37.00  90.00  178
 26  \w     32.00 121.00   0.50    0.05    --   46.87  37.00   0.00  178
 27  \w     32.00 121.00   0.50    0.05    --   46.87  37.00-150.00  178
 28  \w     32.00 121.00   0.50    0.05    --   46.87  37.00 -90.00  178
;
_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      -0.0038286000
_diffrn_orient_matrix_UB_12      -0.0179376000
_diffrn_orient_matrix_UB_13      0.0461529000
_diffrn_orient_matrix_UB_21      -0.1266003000
_diffrn_orient_matrix_UB_22      0.0369246000
_diffrn_orient_matrix_UB_23      0.0017249000
_diffrn_orient_matrix_UB_31      -0.0483844000
_diffrn_orient_matrix_UB_32      -0.0945571000
_diffrn_orient_matrix_UB_33      -0.0080528000
_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  0.0442
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            64485
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.689
_diffrn_reflns_theta_min         2.689
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.655
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.622
_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    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             2256
_exptl_crystal_size_max          0.156
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.093
_refine_diff_density_max         0.257
_refine_diff_density_min         -0.594
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details 'Flack (1983), 9264 Friedel pairs'
_refine_ls_abs_structure_Flack   0.325(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     614
_refine_ls_number_reflns         11422
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.0297
_refine_ls_R_factor_gt           0.0285
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0354P)^2^+2.5044P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0717
_refine_ls_wR_factor_ref         0.0726
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                11051
_reflns_number_total             11422
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c01051_si_003.cif
_cod_data_source_block           hpd162
_cod_database_code               4518677
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H Br O Si N'
_chemical_oxdiff_usercomment     'D10900A Br'
_shelx_estimated_absorpt_t_max   0.790
_shelx_estimated_absorpt_t_min   0.682
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.675(13)
 0.325(13)
2. 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
3.a Ternary CH refined with riding coordinates:
 C45(H45), C42(H42), C22(H22), C48(H48), C16(H16), C19(H19)
3.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C51(H51A,H51B), C27(H27A,H27B), C25(H25A,H25B)
3.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C10(H10), C9(H9), C38(H38), C12(H12), C13(H13), C36(H36), C35(H35)
3.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C15(H15A,H15B,H15C), C43(H43A,H43B,H43C), C24(H24A,H24B,
 H24C), C46(H46A,H46B,H46C), C20(H20A,H20B,H20C), C41(H41A,H41B,H41C), C47(H47A,
 H47B,H47C), C49(H49A,H49B,H49C), C23(H23A,H23B,H23C), C52(H52A,H52B,H52C),
 C44(H44A,H44B,H44C), C50(H50A,H50B,H50C), C18(H18A,H18B,H18C), C26(H26A,H26B,
 H26C), C29(H29A,H29B,H29C), C7(H7A,H7B,H7C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              60436
_shelx_hkl_checksum              37186
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.438
_oxdiff_exptl_absorpt_empirical_full_min 0.740