Synthesis of Enantioenriched Alkylfluorides by the Fluorination of Boronate Complexes.
Sandford, Christopher; Rasappan, Ramesh; Aggarwal, Varinder K.; Journal of the American Chemical Society 137 (2015) 10100–10103; doi:10.1021/jacs.5b05848

data_4129448
_publ_section_title
;
 Synthesis of Enantioenriched Alkylfluorides by the Fluorination of
 Boronate Complexes.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              10100
_journal_page_last               10103
_journal_paper_doi               10.1021/jacs.5b05848
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C33 H61 F O Si'
_chemical_formula_sum            'C33 H61 F O Si'
_chemical_formula_weight         520.90
_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     iterative
_audit_creation_date             2015-05-28
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.145(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.0752(8)
_cell_length_b                   6.2109(2)
_cell_length_c                   23.7697(7)
_cell_measurement_reflns_used    4118
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      20.97
_cell_measurement_theta_min      2.16
_cell_volume                     3255.24(18)
_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, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_device_type  'Bruker Apex II kappa CCD area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0940
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            29802
_diffrn_reflns_point_group_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.867
_diffrn_reflns_theta_min         2.162
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.100
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6526
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0634 before and 0.0533 after correction.
The Ratio of minimum to maximum transmission is 0.8753.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.063
_exptl_crystal_description       block
_exptl_crystal_F_000             1160
_exptl_crystal_size_max          0.52
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.295
_refine_diff_density_min         -0.325
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 2839 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.06(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     806
_refine_ls_number_reflns         14418
_refine_ls_number_restraints     309
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1266
_refine_ls_R_factor_gt           0.0683
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0529P)^2^+1.6311P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1315
_refine_ls_wR_factor_ref         0.1597
_reflns_Friedel_coverage         0.706
_reflns_Friedel_fraction_full    0.870
_reflns_Friedel_fraction_max     0.847
_reflns_number_gt                9210
_reflns_number_total             14418
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b05848_si_002.cif
_cod_data_source_block           testm1
_cod_original_cell_volume        3255.23(18)
_cod_database_code               4129448
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-C34A = C36-C34 = C3_$1-C2_$1 = C3_$1-C1A_$1 = C3_$1-C1_$1
 1.53 with sigma of 0.005
 C48-C47 \\sim C48A-C47 \\sim C49-C48 \\sim C49-C48A
 with sigma of 0.01
 C64A-C63A \\sim C65A-C63A \\sim C66A-C63A \\sim C66-C63 \\sim C64-C63 \\sim
C65-C63
 with sigma of 0.01
 F2-C52 \\sim F2A-C52A
 with sigma of 0.01
 C51A-C50 \\sim C51-C50 \\sim C52A-C51A \\sim C52-C51 \\sim C53-C52A \\sim
C53-C52
 with sigma of 0.01
 C55A-C54 \\sim C55-C54 \\sim C56-C55 \\sim C56-C55A
 with sigma of 0.01
 Si2A-O2 \\sim Si2-O2
 with sigma of 0.01
 Si2A-C61A \\sim Si2A-C62A \\sim Si2-C62 \\sim Si2-C61
 with sigma of 0.01
 Si2-C63 \\sim Si2A-C63A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C34 \\sim C36 \\sim C35 \\sim C34A \\sim C35A: within 2A with sigma of 0.003
and sigma for terminal atoms of 0.006
C2 \\sim C3 \\sim C1 \\sim C1A: within 2A with sigma of 0.003 and sigma for
terminal atoms of 0.006
Si2 \\sim C62 \\sim Si2A \\sim C66 \\sim C65 \\sim C61 \\sim C63 \\sim C63A
\\sim C64 \\sim C62A \\sim C61A \\sim C66A \\sim C64A \\sim C65A: within 2A
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C60) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C55A) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C48A)
\\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(F2A) = Uanis(F2)
4. Others
 Fixed Sof: F2(0.5665) Si2(0.47514) H49A(0.4335) H49(0.5665) C55A(0.4335)
 H55A(0.4335) H55B(0.4335) H47C(0.4335) H47D(0.4335) H47A(0.5665) H47B(0.5665)
 H50(0.5665) H50A(0.4335) C34(0.56673) H34A(0.56673) H34B(0.56673)
 H34C(0.56673) C51(0.5665) H51A(0.5665) H51B(0.5665) C48A(0.4335) H48A(0.4335)
 H48B(0.4335) H36(0.56673) H36A(0.43327) C52(0.5665) H52(0.5665) H53(0.5665)
 H53A(0.4335) H3A(0.46505) H3B(0.53495) C35(0.56673) H35A(0.56673)
 H35B(0.56673) H35C(0.56673) H56C(0.4335) H56D(0.4335) H56A(0.5665)
 H56B(0.5665) C1(0.46505) H1A(0.46505) H1B(0.46505) H1C(0.46505) C62(0.47514)
 H62A(0.47514) H62B(0.47514) H62C(0.47514) Si2A(0.52486) C66(0.47514)
 H66A(0.47514) H66B(0.47514) H66C(0.47514) C65(0.47514) H65A(0.47514)
 H65B(0.47514) H65C(0.47514) C61(0.47514) H61A(0.47514) H61B(0.47514)
 H61C(0.47514) C63(0.47514) C63A(0.52486) C64(0.47514) H64A(0.47514)
 H64B(0.47514) H64C(0.47514) C62A(0.52486) H62D(0.52486) H62E(0.52486)
 H62F(0.52486) C61A(0.52486) H61D(0.52486) H61E(0.52486) H61F(0.52486)
 C66A(0.52486) H66D(0.52486) H66E(0.52486) H66F(0.52486) C64A(0.52486)
 H64D(0.52486) H64E(0.52486) H64F(0.52486) C65A(0.52486) H65D(0.52486)
 H65E(0.52486) H65F(0.52486) C48(0.5665) H48C(0.5665) H48D(0.5665) C51A(0.4335)
 H51C(0.4335) H51D(0.4335) C52A(0.4335) H52A(0.4335) F2A(0.4335) C55(0.5665)
 H55C(0.5665) H55D(0.5665) C1A(0.53495) H1AA(0.53495) H1AB(0.53495)
 H1AC(0.53495) C34A(0.43327) H34D(0.43327) H34E(0.43327) H34F(0.43327)
 C35A(0.43327) H35D(0.43327) H35E(0.43327) H35F(0.43327)
5.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C9(H9), C49(H49A), C49(H49), C17(H17), C42(H42), C57(H57),
  C7(H7), C24(H24), C20(H20), C50(H50), C50(H50A), C12(H12), C45(H45), C40(H40),
  C36(H36), C36(H36A), C52(H52), C53(H53), C53(H53A), C3(H3A), C3(H3B),
 C52A(H52A)
5.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C6(H6A,H6B), C5(H5A,H5B), C4(H4A,H4B), C18(H18A,H18B),
 C10(H10A,H10B), C37(H37A,H37B), C22(H22A,H22B), C15(H15A,H15B), C39(H39A,H39B),
  C44(H44A,H44B), C23(H23A,H23B), C14(H14A,H14B), C55A(H55A,H55B), C47(H47C,
 H47D), C47(H47A,H47B), C43(H43A,H43B), C38(H38A,H38B), C25(H25A,H25B),
 C51(H51A,H51B), C48A(H48A,H48B), C58(H58A,H58B), C56(H56C,H56D), C56(H56A,
 H56B), C48(H48C,H48D), C51A(H51C,H51D), C55(H55C,H55D)
5.c Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C2(H2A,H2B,H2C), C41(H41A,H41B,H41C), C59(H59A,H59B,
 H59C), C34(H34A,H34B,H34C), C27(H27A,H27B,H27C), C26(H26A,H26B,H26C), C33(H33A,
 H33B,H33C), C32(H32A,H32B,H32C), C8(H8A,H8B,H8C), C60(H60A,H60B,H60C),
 C29(H29A,H29B,H29C), C35(H35A,H35B,H35C), C28(H28A,H28B,H28C), C1(H1A,H1B,H1C),
  C62(H62A,H62B,H62C), C66(H66A,H66B,H66C), C65(H65A,H65B,H65C), C61(H61A,H61B,
 H61C), C64(H64A,H64B,H64C), C62A(H62D,H62E,H62F), C61A(H61D,H61E,H61F),
 C66A(H66D,H66E,H66F), C64A(H64D,H64E,H64F), C65A(H65D,H65E,H65F), C1A(H1AA,
 H1AB,H1AC), C34A(H34D,H34E,H34F), C35A(H35D,H35E,H35F)
;
_shelx_res_checksum              22681
_shelx_hkl_checksum              66025
_olex2_submission_special_instructions 'No special instructions were received'