Selective Monodefluorination and Wittig Functionalization of gem-Difluoromethyl Groups to Generate Monofluoroalkenes.
Mandal, Dipendu; Gupta, Richa; Young, Rowan D.; Journal of the American Chemical Society 140 (2018) 10682–10686; doi:10.1021/jacs.8b06770

data_4132813
_publ_section_title
;
 Selective Monodefluorination and Wittig Functionalization of
 gem-Difluoromethyl Groups to Generate Monofluoroalkenes.
;
_journal_issue                   34
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10682
_journal_page_last               10686
_journal_paper_doi               10.1021/jacs.8b06770
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C29 H29 F P, B C18 F16'
_chemical_formula_sum            'C47 H29 B F17 P'
_chemical_formula_weight         958.48
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-04-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                94.145(4)
_cell_angle_beta                 96.365(4)
_cell_angle_gamma                107.952(4)
_cell_formula_units_Z            2
_cell_length_a                   12.5727(15)
_cell_length_b                   13.0829(16)
_cell_length_c                   13.4393(17)
_cell_measurement_reflns_used    6756
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      26.58
_cell_measurement_theta_min      2.46
_cell_volume                     2076.7(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      99.91
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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  0.0634
_diffrn_reflns_av_unetI/netI     0.0655
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            23380
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.735
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.178
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5821
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0830 before and 0.0634 after correction. The Ratio of minimum to maximum transmission is 0.7810. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.533
_exptl_crystal_description       block
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.371
_exptl_crystal_size_mid          0.248
_exptl_crystal_size_min          0.154
_refine_diff_density_max         2.194
_refine_diff_density_min         -0.940
_refine_diff_density_rms         0.100
_refine_ls_extinction_coef       0.0049(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     600
_refine_ls_number_reflns         7285
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.1345
_refine_ls_R_factor_gt           0.0908
_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^)+(0.0969P)^2^+11.1737P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2228
_refine_ls_wR_factor_ref         0.2620
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4845
_reflns_number_total             7285
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b06770_si_001.cif
_cod_data_source_block           mo_ry_dm_1_35_0m
_cod_depositor_comments
;

2020-10-16
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '0.5(C29 H29 F P), 0.5(B C18 F16)'
_cod_original_formula_sum        'C23.50 H14.50 B0.50 F8.50 P0.50'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     479.24
_cod_database_code               4132813
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H11)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H15), C4(H14), C6(H13), C7(H12), C10(H19), C11(H20), C12(H21), C13(H22),
 C17(H26), C18(H27), C19(H28), C20(H29), C24(H33), C25(H34), C26(H35), C27(H36)
2.c Idealised Me refined as rotating group:
 C8(H16,H17,H18), C15(H23,H24,H25), C22(H30,H31,H32), C29(H37,H38,H39)
;
_shelx_res_checksum              71431
_shelx_hkl_checksum              55728
_olex2_submission_original_sample_id RY_DM_1_35
_olex2_submission_special_instructions 'No special instructions were received'