Rhodium-Catalyzed Regioselective Silylation of Alkyl C-H Bonds for the Synthesis of 1,4-Diols.
Karmel, Caleb; Li, Bi-Jie; Hartwig, John F.; Journal of the American Chemical Society  (2018) –; doi:10.1021/jacs.7b11964

data_4127058
_publ_section_title
;
 Rhodium-Catalyzed Regioselective Silylation of Alkyl C-H Bonds for the
 Synthesis of 1,4-Diols.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b11964
_journal_year                    2018
_chemical_formula_moiety         'C53 H57 Cl O2 P2 Rh Si, 0.5(C2 H4 Cl2)'
_chemical_formula_sum            'C54 H59 Cl2 O2 P2 Rh Si'
_chemical_formula_weight         1003.85
_chemical_name_common            compound8
_chemical_name_systematic        compound8
_space_group.centring_type       primitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-11-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                95.114(3)
_cell_angle_beta                 92.970(3)
_cell_angle_gamma                90.036(3)
_cell_formula_units_Z            4
_cell_length_a                   11.5444(5)
_cell_length_b                   16.0589(7)
_cell_length_c                   26.8374(14)
_cell_measurement_reflns_used    9760
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      68.90
_cell_measurement_theta_min      4.12
_cell_volume                     4948.9(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XH (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.944
_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  0.0913
_diffrn_reflns_av_unetI/netI     0.0871
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_refln_scan_rate          10
_diffrn_refln_scan_width         2.0
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            69005
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         69.312
_diffrn_reflns_theta_min         2.763
_diffrn_source                   'microfocus rotating anode'
_exptl_absorpt_coefficient_mu    4.931
_exptl_absorpt_correction_T_max  0.929
_exptl_absorpt_correction_T_min  0.616
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.347
_exptl_crystal_description       prism
_exptl_crystal_F_000             2088
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_platon_squeeze_details          )
_refine_diff_density_max         5.911
_refine_diff_density_min         -1.528
_refine_diff_density_rms         0.195
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1126
_refine_ls_number_reflns         17750
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1193
_refine_ls_R_factor_gt           0.1059
_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^)+(0.1632P)^2^+54.5741P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2772
_refine_ls_wR_factor_ref         0.2935
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15094
_reflns_number_total             17750
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b11964_si_003.cif
_cod_data_source_block           compound8
_cod_database_code               4127058
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.827
_shelx_estimated_absorpt_t_min   0.791
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.79385
 0.20615
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C41) \\sim Ueq, Uanis(C94) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
4.a Ternary CH refined with riding coordinates:
 C46(H46), C48(H48), C50(H50), C99(H99), C101(H101), C103(H103)
4.b Secondary CH2 refined with riding coordinates:
 C40(H40a,H40b), C42(H42a,H42b), C45(H45a,H45b), C47(H47a,H47b), C49(H49a,
 H49b), C51(H51a,H51b), C52(H52a,H52b), C53(H53a,H53b), C93(H93a,H93b),
 C95(H95a,H95b), C98(H98a,H98b), C100(H10a,H10b), C102(H10c,H10d), C104(H10e,
 H10f), C105(H10g,H10h), C106(H10i,H10j), C107(H10k,H10l), C108(H10m,H10n)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C20(H20), C21(H21), C22(H22), C29(H29),
  C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C36(H36), C37(H37),
 C38(H38), C39(H39), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C61(H61),
  C62(H62), C63(H63), C64(H64), C65(H65), C67(H67), C68(H68), C69(H69),
 C73(H73), C74(H74), C75(H75), C82(H82), C83(H83), C84(H84), C85(H85), C86(H86),
  C88(H88), C89(H89), C90(H90), C91(H91), C92(H92)
4.d Idealised Me refined as rotating group:
 C26(H26a,H26b,H26c), C27(H27a,H27b,H27c), C41(H41a,H41b,H41c), C43(H43a,H43b,
 H43c), C79(H79a,H79b,H79c), C80(H80a,H80b,H80c), C94(H94a,H94b,H94c), C96(H96a,
 H96b,H96c)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'