Copper-Catalyzed Ring-Opening Defluorinative Alkylation of Siloxydifluorocyclopropanes: Synthesis of γ-Fluoro-δ-Ketoesters and γ,δ-Diketonitriles.
Wang, Shifang; Liu, Xiaowei; Zhu, Dongsheng; Wang, Mang; The Journal of organic chemistry 85 (2020) 12408–12417; doi:10.1021/acs.joc.0c01643

data_4038763
_publ_section_title
;
 Copper-Catalyzed Ring-Opening Defluorinative Alkylation of
 Siloxydifluorocyclopropanes: Synthesis of \g-Fluoro-\d-Ketoesters and
 \g,\d-Diketonitriles.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12408
_journal_page_last               12417
_journal_paper_doi               10.1021/acs.joc.0c01643
_journal_volume                  85
_journal_year                    2020
_chemical_formula_moiety         'C20 H21 F O3'
_chemical_formula_sum            'C20 H21 F O3'
_chemical_formula_weight         328.37
_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   geom
_audit_creation_date             2019-09-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-07 # Formatted by publCIF

;
_cell_angle_alpha                90
_cell_angle_beta                 91.741(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.058(4)
_cell_length_b                   14.261(3)
_cell_length_c                   6.1046(10)
_cell_measurement_reflns_used    3259
_cell_measurement_temperature    296
_cell_measurement_theta_max      57.000
_cell_measurement_theta_min      1.953
_cell_volume                     1745.4(6)
_computing_cell_refinement       'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      296
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX II'
_diffrn_measurement_method       '0.60\ % \ w and 0.6\ % \ f scans'
_diffrn_radiation_collimation    '0.5 mm double- pinhole'
_diffrn_radiation_detector       'Bruker APEX II'
_diffrn_radiation_monochromator  'equatorially mounted graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0647
_diffrn_reflns_av_unetI/netI     0.0646
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            10499
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        63.684
_diffrn_reflns_theta_max         63.684
_diffrn_reflns_theta_min         2.204
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Siemens, K FFCU 2K 90'
_exptl_absorpt_coefficient_mu    0.738
_exptl_absorpt_correction_T_max  0.86
_exptl_absorpt_correction_T_min  0.84
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.250
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.242
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         2830
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.1192
_refine_ls_R_factor_gt           0.0618
_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^)+(0.0517P)^2^+0.6946P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1216
_refine_ls_wR_factor_ref         0.1416
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1670
_reflns_number_total             2830
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01643_si_002.cif
_cod_data_source_block           1_a
_cod_depositor_comments
'Adding full bibliography for 4038763--4038764.cif.'
_cod_original_cell_volume        1745.4(5)
_cod_database_code               4038763
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.54
_shelx_estimated_absorpt_t_min   0.21
_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:
 C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C00N(H00A,H00B,H00C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              53040
_shelx_hkl_checksum              40667
_olex2_submission_special_instructions 'No special instructions were received'
_publcif_funding_html
;
;