Palladium-Catalyzed/Norbornene-Mediated ortho-Amination/N-Tosylhydrazone Insertion Reaction: An Approach to the Synthesis of ortho-Aminated Vinylarenes.
Zhou, Ping-Xin; Ye, Yu-Ying; Ma, Jun-Wei; Zheng, Lan; Tang, Qian; Qiu, Yi-Feng; Song, Bo; Qiu, Zi-Hang; Xu, Peng-Fei; Liang, Yong-Min; The Journal of organic chemistry 79 (2014) 6627–6633; doi:10.1021/jo501125b

data_4029679
_publ_section_title
;
 Palladium-Catalyzed/Norbornene-Mediated ortho-Amination/N-Tosylhydrazone
 Insertion Reaction: An Approach to the Synthesis of ortho-Aminated
 Vinylarenes.
;
_journal_issue                   14
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6627
_journal_page_last               6633
_journal_paper_doi               10.1021/jo501125b
_journal_volume                  79
_journal_year                    2014
_chemical_formula_moiety         'C22 H25 N O3'
_chemical_formula_sum            'C22 H25 N O3'
_chemical_formula_weight         351.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-03-24
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.12 svn.r2899 for OlexSys, GUI svn.r4796)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 105.111(13)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.3748(8)
_cell_length_b                   19.4128(19)
_cell_length_c                   13.8717(14)
_cell_measurement_reflns_used    2789
_cell_measurement_temperature    294.35(10)
_cell_measurement_theta_max      26.8440
_cell_measurement_theta_min      3.5420
_cell_volume                     1917.3(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      294.35(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0212427000
_diffrn_orient_matrix_UB_12      -0.0291209000
_diffrn_orient_matrix_UB_13      -0.0318758000
_diffrn_orient_matrix_UB_21      0.0918042000
_diffrn_orient_matrix_UB_22      0.0010347000
_diffrn_orient_matrix_UB_23      -0.0069358000
_diffrn_orient_matrix_UB_31      0.0322899000
_diffrn_orient_matrix_UB_32      -0.0220282000
_diffrn_orient_matrix_UB_33      0.0417846000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71000
_diffrn_reflns_av_R_equivalents  0.0403
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            11047
_diffrn_reflns_theta_full        25.99
_diffrn_reflns_theta_max         25.99
_diffrn_reflns_theta_min         3.04
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.080
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61675
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.217
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.39
_exptl_crystal_size_min          0.34
_refine_diff_density_max         0.192
_refine_diff_density_min         -0.135
_refine_diff_density_rms         0.032
_refine_ls_extinction_coef       0.042(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     238
_refine_ls_number_reflns         3608
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0683
_refine_ls_R_factor_gt           0.0488
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0556P)^2^+0.3592P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1217
_refine_ls_wR_factor_ref         0.1373
_reflns_number_gt                2661
_reflns_number_total             3608
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo501125b_si_002.cif
_cod_data_source_block           zhoupx0324
_cod_depositor_comments
'Adding full bibliography for 4029679--4029680.cif.'
_cod_original_cell_volume        1917.3(3)
_cod_database_code               4029679
_reflns_odcompleteness_completeness 95.08
_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.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C22(H22A,H22B,H22C)
;
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'
_olex2_computing_structure_solution_long 'ShelXS (Sheldrick, 2008)'