Development of a Scalable, Chromatography-Free Synthesis of t-Bu-SMS-Phos and Application to the Synthesis of an Important Chiral CF<sub>3</sub>-Alcohol Derivative with High Enantioselectivity Using Rh-Catalyzed Asymmetric Hydrogenation.
Sieber, Joshua D.; Rodriguez, Sonia; Frutos, Rogelio; Buono, Frederic; Zhang, Yongda; Li, Ning; Qu, Bo; Premasiri, Ajith; Li, Zhibin; Han, Zhengxu S.; Xu, Yibo; Byrne, Denis; Haddad, Nizar; Lorenz, Jon; Grinberg, Nelu; Kurouski, Dmitry; Lee, Heewon; Narayanan, Bikshandarkoil; Nummy, Laurence; Mulder, Jason; Brown, Jack D.; Granger, Alice; Gao, Joe; Krawiec, Mariusz; Williams, Zeena; Pennino, Scott; Song, Jinhua J.; Hossain, Azad; Yee, Nathan K.; Busacca, Carl; Roschangar, Frank; Xin, Yanchao; Mao, Zhantong; Zhang, Xinzhu; Hong, Yaping; Senanayake, Chris H.; The Journal of organic chemistry 83 (2018) 1448–1461; doi:10.1021/acs.joc.7b03022

data_4033411
_publ_section_title
;
 Development of a Scalable, Chromatography-Free Synthesis of t-Bu-SMS-Phos
 and Application to the Synthesis of an Important Chiral
 CF<sub>3</sub>-Alcohol Derivative with High Enantioselectivity Using
 Rh-Catalyzed Asymmetric Hydrogenation.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1448
_journal_page_last               1461
_journal_paper_doi               10.1021/acs.joc.7b03022
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H42 O2 P2, 2(B F4)'
_chemical_formula_sum            'C34 H42 B2 F8 O2 P2'
_chemical_formula_weight         718.23
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2017-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.2487(9)
_cell_length_b                   16.8165(14)
_cell_length_c                   19.3106(16)
_cell_measurement_reflns_used    9012
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      64.43
_cell_measurement_theta_min      3.49
_cell_volume                     3652.9(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1161
_diffrn_reflns_av_unetI/netI     0.1006
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            25447
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        64.816
_diffrn_reflns_theta_max         64.816
_diffrn_reflns_theta_min         3.485
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.699
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.5755
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2016/2 (Bruker,2016/2)'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       prism
_exptl_crystal_F_000             1496
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.881
_refine_diff_density_min         -0.421
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 1705 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     462
_refine_ls_number_reflns         5998
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0927
_refine_ls_R_factor_gt           0.0754
_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^)+(0.1393P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1980
_refine_ls_wR_factor_ref         0.2105
_reflns_Friedel_coverage         0.775
_reflns_Friedel_fraction_full    0.966
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                4827
_reflns_number_total             5998
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b03022_si_002.cif
_cod_data_source_block           scx17_051
_cod_depositor_comments          'Adding full bibliography for 4033411.cif.'
_cod_database_code               4033411
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.920
_shelx_estimated_absorpt_t_min   0.876
_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. Restrained distances
 F2A-F2C = F2B-F2D = F2B'-F2D'
 2.25 with sigma of 0.04
 B2-F2A \\sim B2-F2B \\sim B2-F2B' \\sim B2-F2C \\sim B2-F2D \\sim B2-F2D'
 with sigma of 0.02
3. Rigid bond restraints
 F1A, F1B, F1C, F1D, F2A, F2B, F2B', F2C, F2D, F2D'
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F2A \\sim F2B \\sim F2B' \\sim F2C \\sim F2D \\sim F2D': within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
5. Others
 Sof(F2B')=Sof(F2D')=1-FVAR(1)
 Sof(F2B)=Sof(F2D)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38),
  C39(H39), C40(H40), C41(H41)
6.b Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C45(H45A,H45B,
 H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C)
;
_olex2_date_sample_completion    2017-06-20
_olex2_date_sample_data_collection 2017-06-19
_olex2_date_sample_submission    2017-06-12
_olex2_exptl_crystal_mounting_method MicroMount
_olex2_submission_original_sample_id SCX17_051
_olex2_submission_special_instructions 'No special instructions were received'