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_4122139
_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         'C22 H24 Br Cl3 O2'
_chemical_formula_sum            'C22 H24 Br Cl3 O2'
_chemical_formula_weight         506.67
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-12-11
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.11.15 svn.r2834 for OlexSys, GUI svn.r4720)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.1848(16)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.0837(14)
_cell_length_b                   5.7610(7)
_cell_length_c                   18.212(2)
_cell_measurement_reflns_used    5604
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      27.511
_cell_measurement_theta_min      2.474
_cell_volume                     1122.3(2)
_computing_cell_refinement       'SAINT v8.32B (Bruker, 2013)'
_computing_data_collection       'APEX2 v2011.2-4 (Bruker, 2011)'
_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    'XT (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_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  0.0490
_diffrn_reflns_av_unetI/netI     0.0689
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            19633
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.904
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.204
_exptl_absorpt_correction_T_max  0.745553
_exptl_absorpt_correction_T_min  0.447631
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0941 before and 0.0673 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1521 before and 0.0691 after correction.
 The Ratio of minimum to maximum transmission is 0.60.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 19632 reflections, Rint = 0.0490
 (12184 with I > 3sig(I), Rint = 0.0428)
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.499
_exptl_crystal_description       needle
_exptl_crystal_F_000             516
_exptl_crystal_recrystallization_method
'The material was recrystallised from hexane by slow evaporation'
_exptl_crystal_size_max          0.557
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.136
_refine_diff_density_max         1.136
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details
;
 Flack x determined using 1674 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.028(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         4787
_refine_ls_number_restraints     202
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0482
_refine_ls_R_factor_gt           0.0425
_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^)+(0.0427P)^2^+0.3705P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0982
_refine_ls_wR_factor_ref         0.1049
_reflns_Friedel_coverage         0.795
_reflns_Friedel_fraction_full    0.977
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                4370
_reflns_number_total             4787
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja504797x_si_002.cif
_cod_data_source_block           twin5
_cod_depositor_comments
'Adding full bibliography for 4122138--4122139.cif.'
_cod_database_code               4122139
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.754
_shelx_estimated_absorpt_t_min   0.373
_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. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Rigid body (RIGU) restrains
 C4, C7, C20, C8, C9
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C9, C14, C13, C12, C15, C16, C17, C18, C19, C11, C10
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O1, C21, C22, Cl1, Cl3, Cl2
 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:
 C7(H7), C17(H17)
4.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C8(H8A,H8B), C15(H15A,H15B), C16(H16A,H16B)
4.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C14(H14), C3(H3), C5(H5), C13(H13), C2(H2), C11(H11), C10(H10)
4.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C18(H18A,H18B,H18C)
;