Catalyst-Controlled Selective Functionalization of Unactivated C-H Bonds in the Presence of Electronically Activated C-H Bonds.
Liu, Wenbin; Ren, Zhi; Bosse, Aaron T.; Liao, Kuangbiao; Goldstein, Elizabeth L.; Bacsa, John; Musaev, Djamaladdin G.; Stoltz, Brian M.; Davies, Huw M. L.; Journal of the American Chemical Society 140 (2018) 12247–12255; doi:10.1021/jacs.8b07534

data_4132942
_publ_section_title
;
 Catalyst-Controlled Selective Functionalization of Unactivated C-H Bonds
 in the Presence of Electronically Activated C-H Bonds.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12247
_journal_page_last               12255
_journal_paper_doi               10.1021/jacs.8b07534
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H16 Br Cl O2'
_chemical_formula_sum            'C22 H16 Br Cl O2'
_chemical_formula_weight         427.71
_chemical_name_systematic
;        
 (1S)-1-(5-bromo-2-chlorophenyl)-2,2-diphenylcyclopropanecarboxylic acid
;
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-10
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2018.04.26 svn.r3501 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.91980(10)
_cell_length_b                   14.41860(10)
_cell_length_c                   29.7333(2)
_cell_measurement_reflns_used    20231
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      77.9240
_cell_measurement_theta_min      2.9750
_cell_volume                     3824.03(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 HyPix
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w     93.00 170.00   0.50    3.00    --  110.00 125.00   0.00  154
  2  \w    105.00 177.00   0.50    3.00    --  110.00  84.00 156.00  144
  3  \w     94.00 177.00   0.50    3.00    --  110.00  61.00 120.00  166
  4  \w    -62.00  26.00   0.50    0.50    --  -47.12  57.00   0.00  176
  5  \w     36.00 121.00   0.50    0.50    --   47.12  38.00  -8.00  170
  6  \w    -67.00 -42.00   0.50    3.00    --  -88.50  38.00  -8.00   50
  7  \w     92.00 173.00   0.50    3.00    --  110.00  15.00  90.00  162
  8  \w   -119.00 -52.00   0.50    0.50    --  -47.12 -19.00  90.00  134
  9  \w      4.00  35.00   0.50    0.50    --   47.12 -57.00 120.00   62
 10  \w     43.00  89.00   0.50    3.00    --  110.00 -61.00  90.00   92
 11  \w     39.00  88.00   0.50    3.00    --  110.00 -61.00  30.00   98
 12  \w     51.00  88.00   0.50    3.00    --  110.00 -61.00-120.00   74
 13  \w     38.00 106.00   0.50    3.00    --  110.00 -77.00  90.00  136
 14  \w     60.00  86.00   0.50    3.00    --  110.00 -95.00 -30.00   52
 15  \w     51.00  79.00   0.50    0.50    --   47.12-125.00 -60.00   56
 16  \w   -137.00-112.00   0.50    3.00    --  -88.50-132.00 -28.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0181794000
_diffrn_orient_matrix_UB_12      0.0039626000
_diffrn_orient_matrix_UB_13      0.0515107000
_diffrn_orient_matrix_UB_21      -0.1506114000
_diffrn_orient_matrix_UB_22      -0.0510278000
_diffrn_orient_matrix_UB_23      0.0056679000
_diffrn_orient_matrix_UB_31      0.0825835000
_diffrn_orient_matrix_UB_32      -0.0937374000
_diffrn_orient_matrix_UB_33      -0.0009836000
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0333
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            23741
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.913
_diffrn_reflns_theta_min         3.407
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    4.317
_exptl_absorpt_correction_T_max  0.873
_exptl_absorpt_correction_T_min  0.519
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       prism
_exptl_crystal_F_000             1728
_exptl_crystal_recrystallization_method 'slow evaporation of 2% EtOAc in hexane'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.094
_refine_diff_density_max         0.475
_refine_diff_density_min         -0.390
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 3254 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.010(5)
_refine_ls_extinction_coef       0.00019(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     528
_refine_ls_number_reflns         7890
_refine_ls_number_restraints     308
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0253
_refine_ls_R_factor_gt           0.0242
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0291P)^2^+1.1253P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0618
_refine_ls_wR_factor_ref         0.0621
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.947
_reflns_number_gt                7700
_reflns_number_total             7890
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07534_si_002.cif
_cod_data_source_block           wl-s2cl5br-ligand
_cod_database_code               4132942
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C176  H124  Br8  Cl8  O16  '
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All O(H) groups
 At 1.5 times of:
  All H(H) groups
2. Restrained distances
 O1-H1
 0.955 with sigma of 0.002
 H1-O1'
 1.655 with sigma of 0.001
 C3'-H3'B \\sim C3'-H3'A
 with sigma of 0.002
 C3-H3A \\sim C3'-H3'B
 with sigma of 0.002
 C4_2-C1' \\sim C4_3-C1'
 with sigma of 0.001
 C3-H3A \\sim C3-H3B
 with sigma of 0.001
 C2'-C11_5 \\sim C2'-C11_4
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C4_3) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C5_3) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C11_4) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of
0.002
Uiso(H3'B) = Uiso(H3'A)
Uanis(C11_4) = Uanis(C11_5)
Uanis(C16_4) = Uanis(C16_5)
Uanis(C15_4) = Uanis(C15_5)
Uanis(C14_4) = Uanis(C14_5)
Uanis(C13_4) = Uanis(C13_5)
Uanis(C12_4) = Uanis(C12_5)
Uanis(C5_2) = Uanis(C5_3)
Uanis(C4_2) = Uanis(C4_3)
Uanis(C9_2) = Uanis(C9_3)
Uanis(C8_2) = Uanis(C8_3)
Uanis(C7_2) = Uanis(C7_3)
Uanis(C6_2) = Uanis(C6_3)
Uiso(H3A) = Uiso(H3B)
Uiso(H3B) = Uiso(H3'B)
Uanis(Br1_2) = Uanis(Br1_3)
Uanis(Cl1_3) = Uanis(Cl1_2)
4. Rigid body (RIGU) restrains
 Br1_1, Cl1_1, C4_1, C5_1, C6_1, C7_1, C8_1, C9_1
 Br1_2, Cl1_2, C4_2, C5_2, C6_2, C7_2, C8_2, C9_2
 Br1_3, Cl1_3, C4_3, C5_3, C6_3, C7_3, C8_3, C9_3
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
 C11_4, C12_4, C13_4, C14_4, C15_4, C16_4
 C11_5, C12_5, C13_5, C14_5, C15_5, C16_5
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0004
5. Same fragment restrains
{Br1_2, Cl1_2, C4_2, C5_2, C6_2, C7_2, C8_2, C9_2}
{Br1_3, Cl1_3, C4_3, C5_3, C6_3, C7_3, C8_3, C9_3}
as
{Br1_1, Cl1_1, C4_1, C5_1, C6_1, C7_1, C8_1, C9_1} sigma for 1-2: 0.002 1-3:
0.004
{C11_5, C12_5, C13_5, C14_5, C15_5, C16_5}
as
{C11_4, C12_4, C13_4, C14_4, C15_4, C16_4} sigma for 1-2: 0.002 1-3: 0.004
6. Others
 Sof(Br1)=Sof(Cl1)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=
 Sof(C9)=Sof(H9)=1-FVAR(1)
 Sof(Br1)=Sof(Cl1)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=
 Sof(C9)=Sof(H9)=FVAR(1)
 Sof(C11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=
 Sof(H15)=Sof(C16)=Sof(H16)=1-FVAR(2)
 Sof(C11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=
 Sof(H15)=Sof(C16)=Sof(H16)=FVAR(2)
 Fixed X: H1(0.49172)
 Fixed Y: H1(0.25486)
 Fixed Z: H1(0.59948)
7.a Aromatic/amide H refined with riding coordinates:
 C16(H16), C15(H15), C14(H14), C13(H13), C12(H12), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C18'(H18'), C19'(H19'), C20'(H20'), C21'(H21'),
 C22'(H22'), C6(H6), C7(H7), C9(H9), C6(H6), C7(H7), C9(H9), C6(H6), C7(H7),
 C9(H9), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16)
7.b Idealised tetrahedral OH refined as rotating group:
 O2'(H2')
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id WL-S2Cl5Br-ligand
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.312
_oxdiff_exptl_absorpt_empirical_full_min 0.792