Construction of Multiple, Contiguous Quaternary Stereocenters in Acyclic Molecules by Lithiation-Borylation.
Watson, Charlotte G.; Balanta, Angelica; Elford, Tim G.; Essafi, Stéphanie; Harvey, Jeremy N.; Aggarwal, Varinder K.; Journal of the American Chemical Society  (2014) 141203101453003–; doi:10.1021/ja509029h

data_4123024
_publ_section_title
;
 Construction of Multiple, Contiguous Quaternary Stereocenters in Acyclic
 Molecules by Lithiation-Borylation.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141203101453003
_journal_paper_doi               10.1021/ja509029h
_journal_year                    2014
_chemical_formula_moiety         'C22 H26 F3 N O'
_chemical_formula_sum            'C22 H26 F3 N O'
_chemical_formula_weight         377.44
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-07-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.1545(3)
_cell_length_b                   10.4775(3)
_cell_length_c                   38.4179(10)
_cell_measurement_reflns_used    4274
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      21.75
_cell_measurement_theta_min      2.21
_cell_volume                     4087.4(2)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'Bruker Apex II kappa CCDC area detector'
_diffrn_measurement_device_type  'Bruker Apex II kappa CCDC 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  0.0666
_diffrn_reflns_av_unetI/netI     0.0666
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            33524
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.781
_diffrn_reflns_theta_min         1.060
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.093
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6442
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0634 before and 0.0547 after correction. The Ratio
of minimum to maximum transmission is 0.8642. The \l/2 correction
factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_description       block
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.458
_refine_diff_density_min         -0.424
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 2233 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.6(4)
_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     575
_refine_ls_number_reflns         8704
_refine_ls_number_restraints     253
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0813
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0375P)^2^+1.0965P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0929
_refine_ls_wR_factor_ref         0.1047
_reflns_Friedel_coverage         0.774
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                6387
_reflns_number_total             8704
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja509029h_si_006.cif
_cod_data_source_block           testo1
_cod_database_code               4123024
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1A-C22 \\sim F1-C22 \\sim F2A-C22 \\sim F2-C22 \\sim F3A-C22 \\sim F3-C22
 with sigma of 0.01
 C2-C1 \\sim C2A-C1
 with sigma of 0.01
 F4-C44 \\sim F4A-C44 \\sim F5-C44 \\sim F5A-C44 \\sim F6-C44 \\sim F6A-C44
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F2A \\sim F2 \\sim F3A \\sim F3 \\sim F1A \\sim F1: within 1.7A with sigma of
0.003 and sigma for terminal atoms of 0.006
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C2A \\sim C7A \\sim C6A
\\sim C5A \\sim C4A \\sim C3A: within 1.7A with sigma of 0.003 and sigma for
terminal atoms of 0.006
F5 \\sim F5A \\sim F4A \\sim F4 \\sim F6A \\sim F6: within 1.7A with sigma of
0.003 and sigma for terminal atoms of 0.006
Uanis(F4A) \\sim Ueq, Uanis(F4) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(F5) = Uanis(F5A)
4. Others
 Fixed Sof: F1(0.56969) F2(0.56969) F3(0.56969) C2(0.53729) C3(0.53729)
 H3(0.53729) C4(0.53729) H4(0.53729) C5(0.53729) H5(0.53729) C6(0.53729)
 H6(0.53729) C7(0.53729) H7(0.53729) F4(0.636) F5(0.636) F6(0.636) F1A(0.43031)
 F2A(0.43031) F3A(0.43031) C2A(0.46271) C7A(0.46271) H7A(0.46271) C6A(0.46271)
 H6A(0.46271) C5A(0.46271) H5A(0.46271) C4A(0.46271) H4A(0.46271) C3A(0.46271)
 H3A(0.46271) F6A(0.364) F4A(0.364) F5A(0.364)
5.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), N2(H2), C25(H25), C26(H26), C27(H27), C28(H28), C29(H29),
 C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C7A(H7A), C6A(H6A), C5A(H5A),
  C4A(H4A), C3A(H3A)
5.b Fitted hexagon refined as free rotating group:
 C2(C3,C4,C5,C6,C7), C2A(C7A,C6A,C5A,C4A,C3A)
5.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C14(H14A,H14B,H14C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              35189
_shelx_hkl_checksum              56387
_olex2_submission_special_instructions 'No special instructions were received'