Pd-Catalyzed Enantioselective C-H Iodination: Asymmetric Synthesis of Chiral Diarylmethylamines
Ling Chu; Xiao-Chen Wang; Curtis E. Moore; Arnold L. Rheingold; Jin-Quan Yu; Journal of the American Chemical Society 135 (2013) 16344–16347; doi:10.1021/ja408864c

data_4121092
_publ_section_title
;
 Pd-Catalyzed Enantioselective C-H Iodination: Asymmetric Synthesis of
 Chiral Diarylmethylamines
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16344
_journal_page_last               16347
_journal_paper_doi               10.1021/ja408864c
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H15 F3 I N O2 S'
_chemical_formula_sum            'C16 H15 F3 I N O2 S'
_chemical_formula_weight         469.25
_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   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-08-26
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.08.21 svn.r2771 for OlexSys, GUI svn.r4586)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.396(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.0973(9)
_cell_length_b                   12.2302(7)
_cell_length_c                   18.9196(10)
_cell_measurement_reflns_used    9967
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.803
_cell_measurement_theta_min      2.394
_cell_volume                     3493.3(3)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_collection       'Bruker APEX2 v2013-2.0 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXT, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker X8 APEX II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0598
_diffrn_reflns_av_unetI/netI     0.0970
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            39833
_diffrn_reflns_point_group_measured_fraction_full 0.923
_diffrn_reflns_point_group_measured_fraction_max 0.854
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         30.581
_diffrn_reflns_theta_min         1.076
_diffrn_source                   'sealed tube'
_diffrn_source_type              fine-focus
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.991
_exptl_absorpt_correction_T_max  0.0474
_exptl_absorpt_correction_T_min  0.0226
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1175 before and 0.0913 after correction.
The Ratio of minimum to maximum transmission is 0.4768.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            Colorless
_exptl_crystal_colour_primary    Colorless
_exptl_crystal_density_diffrn    1.784
_exptl_crystal_description       Block
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.257
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.053
_refine_diff_density_max         1.358
_refine_diff_density_min         -0.790
_refine_diff_density_rms         0.160
_refine_ls_abs_structure_details
;
 Flack x determined using 3969 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.07(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     842
_refine_ls_number_reflns         18334
_refine_ls_number_restraints     117
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.1026
_refine_ls_R_factor_gt           0.0764
_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^)+(0.1156P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2088
_refine_ls_wR_factor_ref         0.2247
_reflns_Friedel_coverage         0.652
_reflns_Friedel_fraction_full    0.842
_reflns_Friedel_fraction_max     0.704
_reflns_number_gt                12919
_reflns_number_total             18334
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja408864c_si_002.cif
_cod_data_source_block           Yu27
_cod_database_code               4121092
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.902
_shelx_estimated_absorpt_t_min   0.629
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{I1CB, C8C}
{I1C, C8CB}
3. Restrained distances
 I1AB-C3AB
 2 with sigma of 0.02
 C8A-C7A
 1.5 with sigma of 0.02
 C8-C7
 1.5 with sigma of 0.02
 I1BB-C3BB = I1B-C3B
 2 with sigma of 0.02
 C7BB-C8BB
 1.54 with sigma of 0.01
 C7B-C8B
 1.54 with sigma of 0.01
 C2BB-C8BB
 2.6 with sigma of 0.005
 C2C-C1C = C1C-C2CB
 1.5 with sigma of 0.02
4. Rigid bond restraints
 I1AB, I1A, C8AB, C8A, C2AB, C7AB, C6AB, C5AB, C4AB, C3AB, C2A, C3A, C4A, C7AB,
  C3AB, C7A, C1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 I1BB, I1B, C2B, C7B, C6B, C5B, C4B, C3B, C2BB, C3BB, C4BB, C5BB, C6BB, C7BB,
 C1B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8C, I1CB, C7C, C3CB, C2C, C2CB, C7CB, C3C, C6CB, I1C, C8CB, C4C, C5CB, C5C,
 C6C, C4CB
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(C2A) = Uanis(C2AB)
Uanis(C7AB) = Uanis(C3A)
Uanis(C4A) = Uanis(C6AB)
Uanis(C5AB) = Uanis(C7AB)
Uanis(C4AB) = Uanis(C3AB)
Uanis(C3AB) = Uanis(C7A)
Uanis(C2B) = Uanis(C2BB)
Uanis(C7B) = Uanis(C3A)
Uanis(C6B) = Uanis(C7A)
Uanis(C5B) = Uanis(C6B)
Uanis(C3B) = Uanis(C4B)
Uanis(C8) = Uanis(I1') = Uanis(I1)
Uanis(C2BB) = Uanis(C2B)
Uanis(C3BB) = Uanis(C7B)
Uanis(C6B) = Uanis(C4BB)
Uanis(C5B) = Uanis(C5BB)
Uanis(C6BB) = Uanis(C4B)
Uanis(C3B) = Uanis(C7BB)
Uanis(I1B) = Uanis(C8BB)
Uanis(C8B) = Uanis(I1BB)
Uanis(C5A) = Uanis(C4AB)
Uanis(C8AB) = Uanis(I1A)
Uanis(I1AB) = Uanis(C8A)
Uanis(C2C) = Uanis(C2CB)
Uanis(C3C) = Uanis(C7CB)
Uanis(C4C) = Uanis(C6CB)
Uanis(C5CB) = Uanis(C5C)
Uanis(C4CB) = Uanis(C6C)
Uanis(C7C) = Uanis(C3CB)
Uanis(I1CB) = Uanis(C8C)
Uanis(I1C) = Uanis(C8CB)
6. others
 Sof(I1BB)=Sof(H1BB)=Sof(C2BB)=Sof(C3BB)=Sof(C4BB)=Sof(H4BB)=Sof(C5BB)=
 Sof(H5BB)=Sof(C6BB)=Sof(H6BB)=Sof(C7BB)=Sof(C8BB)=Sof(H8BD)=Sof(H8BE)=
 Sof(H8BF)=1-FVAR(1)
 Sof(I1B)=Sof(H1BA)=Sof(C2B)=Sof(C7B)=Sof(C6B)=Sof(H6B)=Sof(C5B)=Sof(H5B)=
 Sof(C4B)=Sof(H4B)=Sof(C3B)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=FVAR(1)
 Sof(I1AB)=Sof(H1AB)=Sof(C2AB)=Sof(C7AB)=Sof(C6AB)=Sof(H6AB)=Sof(C5AB)=
 Sof(H5AB)=Sof(C4AB)=Sof(H4AB)=Sof(C3AB)=Sof(C8AB)=Sof(H8AD)=Sof(H8AE)=
 Sof(H8AF)=1-FVAR(2)
 Sof(I1A)=Sof(H1AA)=Sof(C2A)=Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=FVAR(2)
 Sof(I1CB)=Sof(H1CB)=Sof(C2CB)=Sof(C3CB)=Sof(C4CB)=Sof(H4CB)=Sof(C5CB)=
 Sof(H5CB)=Sof(C6CB)=Sof(H6CB)=Sof(C7CB)=Sof(C8CB)=Sof(H8CD)=Sof(H8CE)=
 Sof(H8CF)=1-FVAR(3)
 Sof(I1C)=Sof(H1CA)=Sof(C2C)=Sof(C7C)=Sof(C6C)=Sof(H6C)=Sof(C5C)=Sof(H5C)=
 Sof(C4C)=Sof(H4C)=Sof(C3C)=Sof(C8C)=Sof(H8CA)=Sof(H8CB)=Sof(H8CC)=FVAR(3)
 Sof(I1')=1-FVAR(4)
 Sof(I1)=FVAR(4)
7.a Riding coordinates:
 N1(H1), N1A(H1A), N1B(H1B), N1C(H1C)
7.b Ternary CH refined with riding coordinates:
 C1(H1D), C1A(H1AB), C1A(H1AA), C1B(H1BA), C1B(H1BB), C1C(H1CA), C1C(H1CB)
7.c Me refined with riding coordinates:
 C8A(H8AA,H8AB,H8AC), C8AB(H8AD,H8AE,H8AF), C8BB(H8BD,H8BE,H8BF), C8C(H8CA,
 H8CB,H8CC), C8CB(H8CD,H8CE,H8CF)
7.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13), C4A(H4A),
 C5A(H5A), C6A(H6A), C6AB(H6AB), C5AB(H5AB), C4AB(H4AB), C10A(H10A), C11A(H11A),
  C12A(H12A), C13A(H13A), C6B(H6B), C5B(H5B), C4B(H4B), C4BB(H4BB), C5BB(H5BB),
 C6BB(H6BB), C10B(H10B), C11B(H11B), C12B(H12B), C13B(H13B), C6C(H6C), C5C(H5C),
  C4C(H4C), C4CB(H4CB), C5CB(H5CB), C6CB(H6CB), C10C(H10C), C11C(H11C),
 C12C(H12C), C13C(H13C)
7.e Fitted hexagon refined as free rotating group:
 C2A(C3A,C4A,C5A,C6A,C7A), C2AB(C7AB,C6AB,C5AB,C4AB,C3AB), C2B(C7B,C6B,C5B,C4B,
 C3B), C2BB(C3BB,C4BB,C5BB,C6BB,C7BB), C2C(C7C,C6C,C5C,C4C,C3C), C2CB(C3CB,C4CB,
 C5CB,C6CB,C7CB)
7.f Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C15(H15J,H15K,H15L), C15A(H15A,H15B,H15C), C8B(H8BA,H8BB,
 H8BC), C15B(H15D,H15E,H15F), C15C(H15G,H15H,H15I)
;
_shelx_res_checksum              37891