Role of sterically demanding chiral dirhodium catalysts in site-selective C-h functionalization of activated primary C-h bonds.
Qin, Changming; Davies, Huw M. L.; Journal of the American Chemical Society 136 (2014) 9792–9796; doi:10.1021/ja504797x

data_4122138
_publ_section_title
;
 Role of sterically demanding chiral dirhodium catalysts in site-selective
 C-h functionalization of activated primary C-h bonds.
;
_journal_issue                   27
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9792
_journal_page_last               9796
_journal_paper_doi               10.1021/ja504797x
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C24 H31 Br O2'
_chemical_formula_sum            'C24 H31 Br O2'
_chemical_formula_weight         431.40
_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     dual
_audit_creation_date             2014-02-11
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.01.22 svn.r2872 for OlexSys, GUI svn.r4747)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   5.7478(16)
_cell_length_b                   19.923(5)
_cell_length_c                   37.012(10)
_cell_measurement_reflns_used    9684
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      28.748
_cell_measurement_theta_min      2.200
_cell_volume                     4238(2)
_computing_cell_refinement       'SAINT v8.32B (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.32B (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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 1.020
_diffrn_measured_fraction_theta_max 1.024
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1062
_diffrn_reflns_av_unetI/netI     0.1307
_diffrn_reflns_Laue_measured_fraction_full 1.020
_diffrn_reflns_Laue_measured_fraction_max 1.024
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            27122
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.014
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.370
_diffrn_reflns_theta_min         1.100
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.956
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.5463
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1404 before and 0.1052 after correction.
The Ratio of minimum to maximum transmission is 0.7324.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_description       plate
_exptl_crystal_F_000             1808
_exptl_crystal_size_max          0.56
_exptl_crystal_size_mid          0.203
_exptl_crystal_size_min          0.102
_refine_diff_density_max         1.026
_refine_diff_density_min         -1.147
_refine_diff_density_rms         0.208
_refine_ls_abs_structure_details
;
 Flack x determined using 2234 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.182(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     496
_refine_ls_number_reflns         8520
_refine_ls_number_restraints     399
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.1457
_refine_ls_R_factor_gt           0.1315
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0106P)^2^+157.2475P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3067
_refine_ls_wR_factor_ref         0.3137
_reflns_Friedel_coverage         0.727
_reflns_Friedel_fraction_full    0.972
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                6951
_reflns_number_total             8520
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja504797x_si_003.cif
_cod_data_source_block           sad
_cod_depositor_comments
'Adding full bibliography for 4122138--4122139.cif.'
_cod_database_code               4122138
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(C6) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.002
Uanis(C4) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.002
Uanis(C22) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.002
Uanis(C10) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.002
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of 0.004 and sigma for
terminal atoms of 0.004
Uanis(C20) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(C5') \\sim Ueq, Uanis(C9') \\sim Ueq, Uanis(C2') \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.005
Uanis(C23') \\sim Ueq, Uanis(C24') \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.005
Uanis(C11') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
3. Rigid body (RIGU) restrains
 C1, Br1, C24, C2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C24, C23, C3, C4, C5
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4, C5, C6, C8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C6, O1, O2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O2, C7
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C8, H8A, C9
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C10, C9, C22
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C22, C21
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C21, C12, C10, C14, C13, C11
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C14, C16, C15
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C13, C17, C18, C19, C12
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C6', O1'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O2', C7', C6'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C8', C9'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C16', C14', C15'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C19', C20'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C6', C5'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C5', C4'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C5', C8', C4'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Br1', C1', C2', C24'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4', C3', C2', C1', C24', C23'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C9', C10', C22', C21', C12', C13', C14'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C13', C14', C17', C18', C19', C12'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4.a Ternary CH refined with riding coordinates:
 C5(H5), C19(H19), C10(H10), C13(H13), C13'(H13'), C10'(H10'), C19'(H19'),
 C5'(H5')
4.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C21(H21A,H21B), C8(H8A,H8B), C11(H11A,H11B), C18(H18A,H18B),
 C17'(H17C,H17D), C8'(H8'A,H8'B), C18'(H18C,H18D), C11'(H11C,H11D), C21'(H21C,
 H21D)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C2(H2), C23(H23), C22(H22), C24(H24), C23'(H23'), C2'(H2'),
 C22'(H22'), C3'(H3'), C24'(H24')
4.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C7(H7A,H7B,
 H7C), C15'(H15D,H15E,H15F), C7'(H7'A,H7'B,H7'C), C20'(H20D,H20E,H20F),
 C16'(H16D,H16E,H16F)
;