Umpolung <i>α</i>-Silylation of Cyclopropyl Acetates via Low-Temperature Catalytic C-C Activation.
Avullala, Thirupataiah; Asgari, Parham; Hua, Yuanda; Bokka, Apparao; Ridlen, Shawn G.; Yum, Kyungsuk; Dias, H. V. Rasika; Jeon, Junha; ACS catalysis 9 (2019) 402–408; doi:10.1021/acscatal.8b04252

data_4515479
_publ_section_title
;
 Umpolung <i>\a</i>-Silylation of Cyclopropyl Acetates via Low-Temperature
 Catalytic C-C Activation.
;
_journal_issue                   1
_journal_name_full               'ACS catalysis'
_journal_page_first              402
_journal_page_last               408
_journal_paper_doi               10.1021/acscatal.8b04252
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C22 H12 B F18 N6 Rh, C7 H8'
_chemical_formula_sum            'C29 H20 B F18 N6 Rh'
_chemical_formula_weight         908.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-02
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.859(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.0106(8)
_cell_length_b                   9.0679(4)
_cell_length_c                   19.7109(9)
_cell_measurement_reflns_used    9686
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      30.57
_cell_measurement_theta_min      3.06
_cell_volume                     3196.1(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      101.05
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0200
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            42504
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.569
_diffrn_reflns_theta_min         2.777
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.674
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6541
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0505 before and 0.0371 after correction.
The Ratio of minimum to maximum transmission is 0.8767.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.887
_exptl_crystal_description       rods
_exptl_crystal_F_000             1792
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.41
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.590
_refine_diff_density_min         -0.598
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     517
_refine_ls_number_reflns         9783
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0272
_refine_ls_R_factor_gt           0.0237
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0248P)^2^+2.2195P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0564
_refine_ls_wR_factor_ref         0.0579
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9012
_reflns_number_total             9783
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b04252_si_002.cif
_cod_data_source_block           rad411_0m_a
_cod_database_code               4515479
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.770
_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:
 C16(H16), C19(H19)
2.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C7(H7), C12(H12), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
2.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'