Pd-Catalyzed Asymmetric Allylic Alkylation of Pyrazol-5-ones with Allylic Alcohols: The Role of the Chiral Phosphoric Acid in C-O Bond Cleavage and Stereocontrol
Zhong-Lin Tao; Wen-Quan Zhang; Dian-Feng Chen; Arafate Adele; Liu-Zhu Gong; Journal of the American Chemical Society 135 (2013) 9255–9258; doi:10.1021/ja402740q

data_4119972
_publ_section_title
;
 Pd-Catalyzed Asymmetric Allylic Alkylation of Pyrazol-5-ones with Allylic
 Alcohols: The Role of the Chiral Phosphoric Acid in C-O Bond Cleavage and
 Stereocontrol
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9255
_journal_page_last               9258
_journal_paper_doi               10.1021/ja402740q
_journal_volume                  135
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_sum            'C26 H23 Br N2 O'
_chemical_formula_weight         459.37
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_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
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_atom_sites_solution_secondary   difmap
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_cell_formula_units_Z            2
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_cell_length_b                   7.7370(4)
_cell_length_c                   16.0848(14)
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_cell_measurement_temperature    290(2)
_cell_measurement_theta_max      29.0416
_cell_measurement_theta_min      2.9292
_cell_volume                     1149.00(16)
_computing_cell_refinement       'CrysAlisPro (Agilent Technologies)'
_computing_data_collection       'CrysAlisPro (Agilent Technologies)'
_computing_data_reduction        'CrysAlisPro (Agilent Technologies)'
_computing_molecular_graphics    'Ortep-3 (L. J. Farrugia, 2001)'
_computing_publication_material  SHELXL-97
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      290(2)
_diffrn_detector_area_resol_mean 15.9149
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Gemini S Ultra, Agilent Technologies'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'Enhance (Mo) x-ray Source'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0416
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_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
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_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -20
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_diffrn_reflns_theta_full        26.37
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         2.94
_exptl_absorpt_coefficient_mu    1.808
_exptl_absorpt_correction_T_max  0.6315
_exptl_absorpt_correction_T_min  0.5622
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.308
_refine_diff_density_min         -0.347
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.031(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3669
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.007
_refine_ls_R_factor_all          0.1374
_refine_ls_R_factor_gt           0.0568
_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^)+(0.0535P)^2^+0.1394P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1133
_refine_ls_wR_factor_ref         0.1463
_reflns_number_gt                1829
_reflns_number_total             3669
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja402740q_si_001.cif
_cod_data_source_block           shelxl
_cod_original_cell_volume        1149.00(15)
_cod_original_sg_symbol_H-M      'P 21'
_cod_database_code               4119972