Scope and Mechanism in Palladium-Catalyzed Isomerizations of Highly Substituted Allylic, Homoallylic, and Alkenyl Alcohols.
Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément; Journal of the American Chemical Society  (2014) 141121132216006–; doi:10.1021/ja508736u

data_4123011
_publ_section_title
;
 Scope and Mechanism in Palladium-Catalyzed Isomerizations of Highly
 Substituted Allylic, Homoallylic, and Alkenyl Alcohols.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141121132216006
_journal_paper_doi               10.1021/ja508736u
_journal_year                    2014
_chemical_formula_moiety         'C22 H21 Cl N O P Pd, C H2 Cl2'
_chemical_formula_sum            'C23 H23 Cl3 N O P Pd'
_chemical_formula_weight         573.14
_chemical_name_systematic
;
 ?
;
_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
_audit_creation_date             2014-06-26
_audit_creation_method
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Olex2 1.2-beta
(compiled 2014.06.23 svn.r2946 for OlexSys, GUI svn.r4855)
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_cell_formula_units_Z            4
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_cell_length_b                   10.6929(3)
_cell_length_c                   17.4010(5)
_cell_measurement_reflns_used    9980
_cell_measurement_temperature    180.00(14)
_cell_measurement_theta_max      72.4670
_cell_measurement_theta_min      3.4110
_cell_volume                     2377.51(12)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS-1997 (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      180.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
  1 omega  -46.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.5615   37.0000  -30.0000 79

  2 omega -127.00  -78.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.5615  178.0000  120.0000 49

  3 omega -103.00  -58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.5615 -152.0000  -42.0000 45

  4 omega  -30.00   28.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.5615   37.0000  -90.0000 58

  5 omega  -50.00   39.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.5615   37.0000 -150.0000 89

  6 omega  -23.00   20.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -37.5615   37.0000   30.0000 43

  7 omega   78.00  126.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       37.5615  178.0000  120.0000 48

  8 omega   17.00   55.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       37.5615  -99.0000  120.0000 38

  9 omega   28.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -30.0000    0.0000 63

 10 omega   28.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -30.0000  -30.0000 32

 11 omega   39.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -30.0000 -150.0000 51

 12 omega  112.00  165.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716   30.0000   60.0000 53

 13 omega   65.00  151.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  178.0000  -90.0000 86

 14 omega   81.00  173.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716   45.0000    0.0000 92

 15 omega   73.00  112.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716 -111.0000   30.0000 39

 16 omega   86.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716 -111.0000  -90.0000 27

 17 omega   25.00  137.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -77.0000 -150.0000 112

 18 omega   34.00   88.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -30.0000  -90.0000 54

 19 omega   28.00   89.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -30.0000   60.0000 61

 20 omega   56.00   86.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -94.0000 -180.0000 30

 21 omega   28.00   55.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716 -111.0000  -90.0000 27

 22 omega   35.00  137.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      108.1716  -77.0000    0.0000 102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0457980000
_diffrn_orient_matrix_UB_12      -0.1330218000
_diffrn_orient_matrix_UB_13      -0.0022778000
_diffrn_orient_matrix_UB_21      -0.1104711000
_diffrn_orient_matrix_UB_22      0.0530754000
_diffrn_orient_matrix_UB_23      -0.0308564000
_diffrn_orient_matrix_UB_31      0.0150859000
_diffrn_orient_matrix_UB_32      -0.0155933000
_diffrn_orient_matrix_UB_33      -0.0850176000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            15242
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.524
_diffrn_reflns_theta_min         3.459
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.155
_exptl_absorpt_correction_T_max  0.487
_exptl_absorpt_correction_T_min  0.114
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.601
_exptl_crystal_description       prism
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.5041
_exptl_crystal_size_mid          0.3057
_exptl_crystal_size_min          0.0886
_refine_diff_density_max         1.191
_refine_diff_density_min         -1.056
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         4641
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0343
_refine_ls_R_factor_gt           0.0328
_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^)+(0.0487P)^2^+3.1158P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
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_refine_ls_wR_factor_ref         0.0864
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4418
_reflns_number_total             4641
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja508736u_si_003.cif
_cod_data_source_block           el3
_cod_original_cell_volume        2377.51(11)
_cod_database_code               4123011
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         'C23 H23 Cl3 N O P Pd'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C6(H6A,H6B), C5(H5A,H5B), C1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C16(H16), C24(H24), C19(H19), C25(H25), C23(H23), C12(H12),
 C11(H11), C13(H13), C20(H20), C10(H10), C17(H17), C22(H22), C26(H26)
2.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C)
;
_olex2_submission_special_instructions 'No special instructions were received'