Selective Construction of Quaternary Stereocentres in Radical Cyclisation Cascades triggered by electron-transfer reduction of amide-type carbonyls
Huang, Huan-Ming; Bonilla, Pablo; Procter, David John; Org. Biomol. Chem.  (2017) –; doi:10.1039/C7OB00739F

data_7155575
_publ_section_title
;
 Selective Construction of Quaternary Stereocentres in Radical Cyclisation
 Cascades triggered by electron-transfer reduction of amide-type carbonyls
;
_journal_name_full               'Org. Biomol. Chem.'
_journal_paper_doi               10.1039/C7OB00739F
_journal_year                    2017
_chemical_formula_moiety         '2(C33 H34 F6 N2 O2), C2.81 H6.52, C3.19 H7.48'
_chemical_formula_sum            'C72 H82 F12 N4 O4'
_chemical_formula_weight         1295.41
_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
_audit_creation_date             2016-06-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2017-01-24 deposited with the CCDC.
2017-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                89.100(5)
_cell_angle_beta                 83.969(5)
_cell_angle_gamma                83.670(5)
_cell_formula_units_Z            2
_cell_length_a                   11.6196(7)
_cell_length_b                   13.8475(8)
_cell_length_c                   21.0449(12)
_cell_measurement_reflns_used    4553
_cell_measurement_temperature    150.02(10)
_cell_measurement_theta_max      23.6070
_cell_measurement_theta_min      3.7190
_cell_volume                     3346.9(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.02(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.822
_diffrn_measurement_details
;
  1 omega  -14.00   81.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       18.8601   19.0000  -90.0000 95

  2 omega   22.00   61.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       18.8601  -99.0000 -120.0000 39

  3 omega  -50.00   40.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -       18.8601  -57.0000   90.0000 90

  4 omega  -86.00   11.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      -17.7663  -77.0000  -30.0000 97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0393929000
_diffrn_orient_matrix_UB_12      0.0101601000
_diffrn_orient_matrix_UB_13      -0.0234131000
_diffrn_orient_matrix_UB_21      0.0435313000
_diffrn_orient_matrix_UB_22      -0.0193250000
_diffrn_orient_matrix_UB_23      -0.0239912000
_diffrn_orient_matrix_UB_31      -0.0191474000
_diffrn_orient_matrix_UB_32      -0.0466836000
_diffrn_orient_matrix_UB_33      0.0049917000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0452
_diffrn_reflns_av_unetI/netI     0.1002
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.822
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            22758
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.822
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.254
_diffrn_reflns_theta_min         3.268
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.102
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88190
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.285
_exptl_crystal_description       block
_exptl_crystal_F_000             1364
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.896
_refine_diff_density_min         -0.784
_refine_diff_density_rms         0.069
_refine_ls_extinction_coef       0.0079(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     866
_refine_ls_number_reflns         14966
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.1656
_refine_ls_R_factor_gt           0.0950
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1053P)^2^+3.4579P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2256
_refine_ls_wR_factor_ref         0.2787
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7852
_reflns_number_total             14966
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ob00739f2.cif
_cod_data_source_block           ahhm031
_cod_database_code               7155575
_chemical_oxdiff_formula         C30H30N2O3F6
_chemical_oxdiff_usercomment     'NDMG2 for MG/STL'
_reflns_odcompleteness_completeness 98.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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(C68A) = Uanis(C68B)
Uanis(C69A) = Uanis(C69B)
Uanis(C67A) = Uanis(C67B)
Uanis(C70A) = Uanis(C70B)
Uanis(C71A) = Uanis(C71B)
Uanis(C72A) = Uanis(C72B)
Uanis(F3) = Uanis(F2) = Uanis(F1)
Uanis(C7B) = Uanis(C6B)
Uanis(F10) = Uanis(F10A)
Uanis(F11) = Uanis(F11A)
Uanis(F12) = Uanis(F12A)
Uanis(F10) = Uanis(F11)
3. Others
 Sof(C71B)=Sof(H71A)=Sof(H71B)=Sof(C67B)=Sof(H67D)=Sof(H67E)=Sof(H67F)=
 Sof(C68B)=Sof(H68C)=Sof(H68D)=Sof(C69B)=Sof(H69C)=Sof(H69D)=Sof(C70B)=
 Sof(H70C)=Sof(H70D)=Sof(C72B)=Sof(H72D)=Sof(H72E)=Sof(H72F)=1-FVAR(1)
 Sof(C67A)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C68A)=Sof(H68A)=Sof(H68B)=
 Sof(C69A)=Sof(H69A)=Sof(H69B)=Sof(C70A)=Sof(H70A)=Sof(H70B)=Sof(C72A)=
 Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C71A)=Sof(H71C)=Sof(H71D)=FVAR(1)
 Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=1-FVAR(2)
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=FVAR(2)
 Sof(F12A)=Sof(F11A)=Sof(F10A)=1-FVAR(3)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(3)
4.a Ternary CH refined with riding coordinates:
 C14(H14), C52(H52)
4.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C17(H17A,H17B), C18(H18A,H18B), C22(H22A,H22B), C25(H25A,
 H25B), C26(H26A,H26B), C41(H41A,H41B), C43(H43A,H43B), C45(H45A,H45B),
 C48(H48A,H48B), C49(H49A,H49B), C56(H56A,H56B), C68A(H68A,H68B), C69A(H69A,
 H69B), C70A(H70A,H70B), C71B(H71A,H71B), C68B(H68C,H68D), C69B(H69C,H69D),
 C70B(H70C,H70D), C71A(H71C,H71D)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C8(H8), C28(H28), C29(H29), C31(H31), C32(H32), C36(H36),
 C37(H37), C39(H39), C40(H40), C59(H59), C61(H61), C62(H62), C64(H64), C65(H65),
  C6B(H6B), C7B(H7B), C6A(H6A), C7A(H7A)
4.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C24(H24A,H24B,
 H24C), C44(H44A,H44B,H44C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C58(H58A,
 H58B,H58C), C67A(H67A,H67B,H67C), C72A(H72A,H72B,H72C), C67B(H67D,H67E,H67F),
 C72B(H72D,H72E,H72F)
;
_shelx_res_checksum              17249
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-06-12
_olex2_submission_special_instructions 'No special instructions were received'