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_4132943
_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         'C34 H42 F6 O4'
_chemical_formula_sum            'C34 H42 F6 O4'
_chemical_formula_weight         628.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           3
_space_group_name_Hall           'P 2y'
_space_group_name_H-M_alt        'P 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-28
_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                 117.4652(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.1525(4)
_cell_length_b                   5.53398(4)
_cell_length_c                   27.2474(4)
_cell_measurement_reflns_used    24772
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.5070
_cell_measurement_theta_min      3.2370
_cell_volume                     3365.19(10)
_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 0.987
_diffrn_measured_fraction_theta_max 0.968
_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    -56.00  31.00   0.50    3.50    --  -41.49  38.00 -30.00  174
  2  \w   -113.00 -26.00   0.50    3.50    --  -41.24 -47.00  52.00  174
  3  \w    -55.00  31.00   0.50    3.50    --  -41.24  47.00-158.00  172
  4  \w   -101.00 -75.00   0.50    3.50    --  -41.24 -57.00 -60.00   52
  5  \w   -113.00 -34.00   0.50    3.50    --  -41.24 -57.00  30.00  158
  6  \w   -114.00 -38.00   0.50    3.50    --  -41.24 -57.00 -30.00  152
  7  \w      5.00  30.00   0.50    3.50    --   41.71 -99.00-120.00   50
  8  \w     60.00 107.00   0.50    3.50    --   41.71 178.00  60.00   94
  9  \w     39.00  71.00   0.50    3.50    --   41.71 -99.00-120.00   64
 10  \w    -29.00  30.00   0.50    3.70    --   41.71 -77.00 150.00  118
 11  \w     26.00  98.00   0.50    3.70    --   41.71  77.00 -60.00  144
 12  \w     -4.00  22.00   0.50    3.70    --   41.71 -38.00 150.00   52
 13  \w     68.00 113.00   0.50    3.70    --   41.71 178.00   0.00   90
 14  \w    -78.00 -16.00   0.50   10.00    --  -88.50  95.00 -56.00  124
 15  \w   -103.00 -77.00   0.50    3.70    --  -47.12-125.00 -90.00   52
 16  \w     75.00 102.00   0.50    3.70    --   47.12  57.00   0.00   54
 17  \w     52.00  79.00   0.50    3.70    --   47.12 -99.00   0.00   54
 18  \w   -130.00 -72.00   0.50   10.00    --  -88.50 -57.00  30.00  116
 19  \w     30.00  86.00   0.50   10.00    --  101.48 -57.00-150.00  112
 20  \w     74.00 101.00   0.50   10.00    --  101.48 -99.00  30.00   54
 21  \w     88.00 126.00   0.50   10.00    --  101.48  38.00  30.00   76
 22  \w     36.00  62.00   0.50   10.00    --  101.48-125.00-120.00   52
 23  \w     89.00 175.00   0.50   10.00    --  101.48  38.00-180.00  172
 24  \w     86.00 117.00   0.50   10.00    --  101.48-125.00-120.00   62
 25  \w     32.00  86.00   0.50   10.00    --  101.48 -57.00  30.00  108
 26  \w     34.00 113.00   0.50   10.00    --  101.48-125.00  30.00  158
 27  \w     94.00 143.00   0.50   10.00    --  101.48  19.00  90.00   98
 28  \w     41.00  86.00   0.50   10.00    --  101.48 -57.00 120.00   90
 29  \w     30.00  67.00   0.50   10.00    --  101.48 -57.00-180.00   74
 30  \w     42.00  78.00   0.50   10.00    --  101.48 -57.00-120.00   72
 31  \w     85.00 154.00   0.50   10.00    --  101.48  57.00   0.00  138
 32  \w     29.00  69.00   0.50   10.00    --  101.48 -99.00  60.00   80
 33  \w     83.00 109.00   0.50   10.00    --  101.48 -99.00  60.00   52
 34  \w    133.00 175.00   0.50   10.00    --  101.48  38.00  30.00   84
 35  \w     39.00  65.00   0.50   10.00    --  101.48 -38.00-150.00   52
 36  \w     68.00 113.00   0.50   10.00    --  101.48 -38.00-150.00   90
 37  \w     43.00 107.00   0.50   10.00    --  101.48 -77.00 120.00  128
 38  \w     34.00  60.00   0.50   10.00    --  101.48 -57.00   0.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0427283000
_diffrn_orient_matrix_UB_12      0.0976866000
_diffrn_orient_matrix_UB_13      0.0215190000
_diffrn_orient_matrix_UB_21      0.0368229000
_diffrn_orient_matrix_UB_22      -0.1303905000
_diffrn_orient_matrix_UB_23      0.0555132000
_diffrn_orient_matrix_UB_31      0.0397668000
_diffrn_orient_matrix_UB_32      0.2257518000
_diffrn_orient_matrix_UB_33      0.0227413000
_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  0.0510
_diffrn_reflns_av_unetI/netI     0.0423
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            42058
_diffrn_reflns_point_group_measured_fraction_full 0.836
_diffrn_reflns_point_group_measured_fraction_max 0.804
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.814
_diffrn_reflns_theta_min         1.980
_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    0.866
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.487
_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    1.241
_exptl_crystal_description       needle
_exptl_crystal_F_000             1328
_exptl_crystal_recrystallization_method
'The material was recrystallised from hexane by slow evaporation'
_exptl_crystal_size_max          0.568
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.038
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.205
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 3112 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.985
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     797
_refine_ls_number_reflns         10947
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.985
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0363
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0388P)^2^+1.0793P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0853
_refine_ls_wR_factor_ref         0.0885
_reflns_Friedel_coverage         0.498
_reflns_Friedel_fraction_full    0.647
_reflns_Friedel_fraction_max     0.599
_reflns_number_gt                9975
_reflns_number_total             10947
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07534_si_006.cif
_cod_data_source_block           aaron-macrocycle_p2
_cod_original_cell_volume        3365.19(9)
_cod_database_code               4132943
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C34 H42 F6  O4  '
_reflns_odcompleteness_completeness 98.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.29
_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.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C12(H12), C13(H13), C1B(H1B), C2B(H2B), C12B(H12B), C13B(H13B)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B),
  C29(H29A,H29B), C33(H33A,H33B), C7B(H7BA,H7BB), C8B(H8BA,H8BB), C9B(H9BA,
 H9BB), C10B(H10C,H10D), C11B(H11C,H11D), C18B(H18C,H18D), C19B(H19C,H19D),
 C20B(H20C,H20D), C21B(H21C,H21D), C22B(H22C,H22D), C29B(H29C,H29D), C33B(H33C,
 H33D)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C15(H15), C16(H16), C23(H23), C24(H24), C25(H25), C26(H26),
 C4B(H4B), C5B(H5B), C15B(H15B), C16B(H16B), C23B(H23B), C24B(H24B), C25B(H25B),
  C26B(H26B)
2.d Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C31(H31A,H31B,H31C), C27B(H27D,H27E,H27F), C31B(H31D,
 H31E,H31F)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method 'The crystal was mounted on a loop'
_olex2_submission_original_sample_id Aaron-macrocycle_P2
_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 1.294
_oxdiff_exptl_absorpt_empirical_full_min 0.703