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_4029680
_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         'C19 H21 N O'
_chemical_formula_sum            'C19 H21 N O'
_chemical_formula_weight         279.37
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-04-09
_audit_creation_method
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Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
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_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.7432(5)
_cell_length_b                   7.9837(5)
_cell_length_c                   30.723(2)
_cell_measurement_reflns_used    933
_cell_measurement_temperature    294.26(10)
_cell_measurement_theta_max      20.9100
_cell_measurement_theta_min      3.6710
_cell_volume                     1653.99(19)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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_computing_data_reduction
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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      294.26(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0024830000
_diffrn_orient_matrix_UB_12      0.0852549000
_diffrn_orient_matrix_UB_13      0.0064809000
_diffrn_orient_matrix_UB_21      -0.0573288000
_diffrn_orient_matrix_UB_22      0.0198942000
_diffrn_orient_matrix_UB_23      -0.0186443000
_diffrn_orient_matrix_UB_31      -0.0881392000
_diffrn_orient_matrix_UB_32      -0.0153635000
_diffrn_orient_matrix_UB_33      0.0119601000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0687
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            4752
_diffrn_reflns_point_group_measured_fraction_full 0.914
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         26.019
_diffrn_reflns_theta_min         3.093
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.069
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46604
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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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    1.122
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.167
_refine_diff_density_min         -0.127
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 441 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   2.6(10)
_refine_ls_extinction_coef       0.011(2)
_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   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         2964
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.1084
_refine_ls_R_factor_gt           0.0631
_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^)+(0.0455P)^2^+0.1717P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1310
_refine_ls_wR_factor_ref         0.1613
_reflns_Friedel_coverage         0.548
_reflns_Friedel_fraction_full    0.794
_reflns_Friedel_fraction_max     0.782
_reflns_number_gt                1717
_reflns_number_total             2964
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo501125b_si_001.cif
_cod_data_source_block           zhoupx0403
_cod_depositor_comments
'Adding full bibliography for 4029679--4029680.cif.'
_cod_original_cell_volume        1654.0(2)
_cod_database_code               4029680
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.65
_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:
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12)
2.c X=CH2 refined with riding coordinates:
 C21(H21A,H21B)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C)
;
_shelx_res_checksum              35900
_shelx_hkl_checksum              73272