Palladium-Catalyzed Ring-Opening Coupling of <i>gem</i>-Difluorocyclopropanes for the Construction of 2-Fluoroallylic Sulfones.
Ni, Jiabin; Nishonov, Bekzod; Pardaev, Azizbek; Zhang, Ao; The Journal of organic chemistry 84 (2019) 13646–13654; doi:10.1021/acs.joc.9b01897

data_4034523
_publ_section_title
;
 Palladium-Catalyzed Ring-Opening Coupling of
 <i>gem</i>-Difluorocyclopropanes for the Construction of 2-Fluoroallylic
 Sulfones.
;
_journal_issue                   21
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              13646
_journal_page_last               13654
_journal_paper_doi               10.1021/acs.joc.9b01897
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C19 H15 F O2 S'
_chemical_formula_sum            'C19 H15 F O2 S'
_chemical_formula_weight         326.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-23
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.521(2)
_cell_length_b                   5.6665(13)
_cell_length_c                   32.043(9)
_cell_measurement_reflns_used    552
_cell_measurement_temperature    220
_cell_measurement_theta_max      19.887
_cell_measurement_theta_min      2.542
_cell_volume                     1547.2(7)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      220
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0826
_diffrn_reflns_av_unetI/netI     0.0903
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            9732
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.393
_diffrn_reflns_theta_min         2.543
_exptl_absorpt_coefficient_mu    0.227
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6436
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0752 before and 0.0607 after correction. The Ratio of minimum to maximum transmission is 0.8633. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.233
_refine_diff_density_min         -0.253
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 776 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.08(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.993
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     208
_refine_ls_number_reflns         3381
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.004
_refine_ls_R_factor_all          0.0864
_refine_ls_R_factor_gt           0.0538
_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^)+(0.0347P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0965
_refine_ls_wR_factor_ref         0.1140
_reflns_Friedel_coverage         0.909
_reflns_Friedel_fraction_full    0.951
_reflns_Friedel_fraction_max     0.931
_reflns_number_gt                2364
_reflns_number_total             3381
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01897_si_002.cif
_cod_data_source_block           mo_20181131njb_0m
_cod_original_cell_volume        1547.1(7)
_cod_database_code               4034523
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.958
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
3.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
3.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C15(H15), C16(H16), C13(H13), C11(H11), C14(H14), C9(H9), C5(H5),
 C19(H19), C4(H4), C3(H3), C2(H2), C1(H1)
;
_olex2_submission_special_instructions 'No special instructions were received'