Catalytic Asymmetric C(sp3)–H Carbene Insertion Approach to Access Enantioenriched 3-Fluoroalkyl 2,3-Dihydrobenzofurans
Zhang, Xinyu; Sivaguru, Paramasivam; Zanoni, Giuseppe; Han, Xinyue; Tong, Minghui; Bi, Xihe; ACS Catalysis 11 (2021) 14293–14301; doi:10.1021/acscatal.1c04523

data_4519168
_publ_section_title
;
 Catalytic Asymmetric C(sp3)--H Carbene Insertion Approach to Access
 Enantioenriched 3-Fluoroalkyl 2,3-Dihydrobenzofurans
;
_journal_issue                   22
_journal_name_full               'ACS Catalysis'
_journal_page_first              14293
_journal_page_last               14301
_journal_paper_doi               10.1021/acscatal.1c04523
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C15 H15 F3 O'
_chemical_formula_sum            'C15 H15 F3 O'
_chemical_formula_weight         268.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.17(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.697(4)
_cell_length_b                   5.5963(19)
_cell_length_c                   12.344(4)
_cell_measurement_reflns_used    804
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      23.8200
_cell_measurement_theta_min      4.1490
_cell_volume                     679.4(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.38a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.38a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.38a (Rigaku OD, 2017)'
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2375
_diffrn_detector_type            Ruby
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.841
_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    -82.00  16.00   1.00    2.21    --   -9.92 -57.00-180.00   98
  2  \w    -99.00 -35.00   1.00    2.21    --   -9.92-178.00 -60.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0688368000
_diffrn_orient_matrix_UB_12      -0.0105476000
_diffrn_orient_matrix_UB_13      -0.0397241000
_diffrn_orient_matrix_UB_21      -0.0056395000
_diffrn_orient_matrix_UB_22      0.1264322000
_diffrn_orient_matrix_UB_23      -0.0036628000
_diffrn_orient_matrix_UB_31      0.0204068000
_diffrn_orient_matrix_UB_32      -0.0008035000
_diffrn_orient_matrix_UB_33      -0.0481546000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0182
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.841
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            3143
_diffrn_reflns_point_group_measured_fraction_full 0.787
_diffrn_reflns_point_group_measured_fraction_max 0.628
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.434
_diffrn_reflns_theta_min         3.591
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.109
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53173
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.38a (Rigaku Oxford Diffraction, 2017)
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    1.311
_exptl_crystal_description       block
_exptl_crystal_F_000             280
_refine_diff_density_max         0.166
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 434 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.2(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     173
_refine_ls_number_reflns         2368
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0754
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0591P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1042
_refine_ls_wR_factor_ref         0.1261
_reflns_Friedel_coverage         0.362
_reflns_Friedel_fraction_full    0.530
_reflns_Friedel_fraction_max     0.369
_reflns_number_gt                1675
_reflns_number_total             2368
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04523_si_001.cif
_cod_data_source_block           210409-bxh02-pwy
_cod_original_cell_volume        679.4(4)
_cod_database_code               4519168
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.09
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Ternary CH refined with riding coordinates:
 C006(H006), C007(H007)
2.b Secondary CH2 refined with riding coordinates:
 C00F(H00A,H00B), C00G(H00E,H00F), C00H(H00G,H00H)
2.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00C(H00C), C00D(H00D)
2.d Idealised Me refined as rotating group:
 C00J(H00I,H00J,H00K)
2.e :
 C1(H1)
;
_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 1.720
_oxdiff_exptl_absorpt_empirical_full_min 0.526