Pd-Catalyzed Semmler-Wolff Reactions for the Conversion of Substituted Cyclohexenone Oximes to Primary Anilines
Wan Pyo Hong; Andrei V. Iosub; Shannon S. Stahl; Journal of the American Chemical Society 135 (2013) 13664–13667; doi:10.1021/ja4073172

data_4120819
_publ_contact_author_address
;
1101 University Ave.
Madison, WI 53706
;
_publ_contact_author_email       stahl@chem.wisc.edu
_publ_contact_author_name        'Shannon Stahl'
_publ_section_title
;
 Pd-Catalyzed Semmler-Wolff Reactions for the Conversion of Substituted
 Cyclohexenone Oximes to Primary Anilines
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13664
_journal_page_last               13667
_journal_paper_doi               10.1021/ja4073172
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety
'C53 H76 F5 N O2 P2 Pd, 0.53(C5 H12), 0.47(C H2 Cl2)'
_chemical_formula_sum            'C56.11 H83.29 Cl0.94 F5 N O2 P2 Pd'
_chemical_formula_weight         1100.65
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_symmetry_space_group_name_Hall  '-P 2yb'
_symmetry_space_group_name_H-M   'P 1 21/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2013-01-25
_audit_creation_method
;
  Olex2 1.2-alpha
  (compiled Nov  5 2012 18:25:38, GUI svn.r4372)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.35(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.671(4)
_cell_length_b                   16.829(7)
_cell_length_c                   16.875(7)
_cell_measurement_reflns_used    9898
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.27
_cell_measurement_theta_min      2.32
_cell_volume                     2730(2)
_computing_cell_refinement       'SAINT+ Ver. 7.68A (Bruker-AXS, 2009)'
_computing_data_collection       'APEX2 Ver. 2012.14-3 (Bruker-AXS, 2012)'
_computing_data_reduction        'SAINT+ Ver. 7.68A'
_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  SHELXTL
_computing_structure_solution    'SHELXTL (Sheldrick, 2008-2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            37509
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.390
_diffrn_reflns_theta_min         1.214
_diffrn_source                   'microfocus sealed x-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.503
_exptl_absorpt_correction_T_max  0.9928
_exptl_absorpt_correction_T_min  0.9216
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0760 before and 0.0482 after correction.
The Ratio of minimum to maximum transmission is 0.9283.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_description       block
_exptl_crystal_F_000             1160
_exptl_crystal_size_max          0.135
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_min          0.058
_refine_diff_density_max         1.247
_refine_diff_density_min         -0.579
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     425
_refine_ls_number_reflns         5718
_refine_ls_number_restraints     247
_refine_ls_restrained_S_all      2.619
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0396
_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^)+(0.0372P)^2^+4.3638P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0934
_refine_ls_wR_factor_ref         0.0973
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5049
_reflns_number_total             5718
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja4073172_si_001.cif
_cod_data_source_block           Stahl159
_cod_original_cell_volume        2729.6(18)
_cod_database_code               4120819
_cod_database_fobs_code          4120819
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H17A,H17B} of C17, {H18A,H18B} of C18, H7 of C7, {H12A,H12B} of C12, {H4A,
  H4B} of C4, {H8A,H8B} of C8, {H5A,H5B} of C5, {H3A,H3B} of C3, {H14A,H14B} of
  C14, {H9A,H9B} of C9, {H15A,H15B} of C15, {H16A,H16B} of C16, {H11A,H11B} of
  C11, {H10A,H10B} of C10, H13 of C13, {H6A,H6B} of C6, {H2A,H2B} of C2, H1 of
  C1, H30 of C30, H29 of C29, {H26A,H26B} of C26, {H25A,H25B} of C25, {H27A,
  H27B} of C27, {H3SA,H3SB} of C3S, {H2SA,H2SB} of C2S, H32A of C32A, H31A of
  C31A, H30A of C30A, H29A of C29A, {H27C,H27D} of C27A, {H26C,H26D} of C26A,
  {H25C,H25D} of C25A, H32 of C32, H31 of C31, {H6SA,H6SB} of C6S, {H4SA,H4SB}
  of C4S
 At 1.5 times of:
  {H1SA,H1SB,H1SC} of C1S, {H5SA,H5SB,H5SC} of C5S
2. Restrained distances
 C6S-Cl2S ~ C6S-Cl1S
 with sigma of 0.0005
3. Uiso/Uaniso restraints and constraints
N1 ~ C24 ~ C25 ~ C26 ~ C27 ~ C28 ~ C29 ~ C30 ~ C31 ~ C32 ~ C33 ~ N1A ~ C24A 
~ C25A ~ C26A ~ C27A ~ C28A ~ C29A ~ C30A ~ C31A ~ C32A ~ C33A: within 1.7A 
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C6S) ~ Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. others
 Sof(N1)=Sof(C24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=
 Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=
 1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-
 Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-
 Sof(C24)=1-Sof(C24)=1-Sof(C24)=1-Sof(C24)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=
 Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=
 Sof(H5SC)=1-Sof(H1SA)=1-Sof(H1SA)=1-Sof(H1SA)=1-Sof(H1SA)=1-Sof(H1SA)
5.a Free rotating group:
 N1(C24,C25,C26,C27,C28,C29,C30,C31,C32,C33), N1A(C24A,C25A,C26A,C27A,C28A,
 C29A,C30A,C31A,C32A,C33A), C1S(C2S,C3S,C4S,C5S,Cl2S,Cl1S,C6S)
5.b Ternary CH refined with riding coordinates:
 C1(H1), C7(H7), C13(H13)
5.c Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B),
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C25(H25A,H25B),
  C26(H26A,H26B), C27(H27A,H27B), C25A(H25C,H25D), C26A(H26C,H26D), C27A(H27C,
 H27D), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C6S(H6SA,H6SB)
5.d Aromatic/amide H refined with riding coordinates:
 C29(H29), C30(H30), C31(H31), C32(H32), C29A(H29A), C30A(H30A), C31A(H31A),
 C32A(H32A)
5.e Idealised Me refined with riding coordinates:
 C1S(H1SA,H1SB,H1SC), C5S(H5SA,H5SB,H5SC)
;
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.935
_shelxl_version_number           2012-6