Highly Enantioselective Allylic C-H Alkylation of Terminal Olefins with Pyrazol-5-ones Enabled by Cooperative Catalysis of Palladium Complex and Brønsted Acid.
Lin, Hua-Chen; Wang, Pu-Sheng; Tao, Zhong-Lin; Chen, Yu-Gen; Han, Zhi-Yong; Gong, Liu-Zhu; Journal of the American Chemical Society 138 (2016) 14354–14361; doi:10.1021/jacs.6b08236

data_4130972
_publ_section_title
;
 Highly Enantioselective Allylic C-H Alkylation of Terminal Olefins with
 Pyrazol-5-ones Enabled by Cooperative Catalysis of Palladium Complex and
 Br\/onsted Acid.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14354
_journal_page_last               14361
_journal_paper_doi               10.1021/jacs.6b08236
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C31 H28 N2 O'
_chemical_formula_sum            'C31 H28 N2 O'
_chemical_formula_weight         444.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.454(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.8305(13)
_cell_length_b                   7.1725(9)
_cell_length_c                   18.792(3)
_cell_measurement_reflns_used    2898
_cell_measurement_temperature    296
_cell_measurement_theta_max      65.05
_cell_measurement_theta_min      4.50
_cell_volume                     1324.6(3)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      296
_diffrn_measured_fraction_theta_full 0.918
_diffrn_measured_fraction_theta_max 0.940
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0888
_diffrn_reflns_av_unetI/netI     0.1181
_diffrn_reflns_Laue_measured_fraction_full 0.918
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            9538
_diffrn_reflns_point_group_measured_fraction_full 0.845
_diffrn_reflns_point_group_measured_fraction_max 0.866
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.640
_diffrn_reflns_theta_min         4.499
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.522
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.2994
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2008/4 (Bruker,2010) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1776 before and 0.1067 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.2025 before and 0.0544 after correction.
 The Ratio of minimum to maximum transmission is 0.27.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 17800 reflections, Rint = 0.3767
 (5010 with I > 3sig(I), Rint = 0.3168)
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.115
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.324
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 786 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.997
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         4064
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.997
_refine_ls_R_factor_all          0.1230
_refine_ls_R_factor_gt           0.0926
_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^)+(0.1634P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2248
_refine_ls_wR_factor_ref         0.2568
_reflns_Friedel_coverage         0.695
_reflns_Friedel_fraction_full    0.759
_reflns_Friedel_fraction_max     0.778
_reflns_number_gt                2746
_reflns_number_total             4064
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b08236_si_002.cif
_cod_data_source_block           cu_dm16425_0m
_cod_original_cell_volume        1324.5(3)
_cod_database_code               4130972
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.950
_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:
 C12(H12A,H12B), C25(H25A,H25B)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14), C16(H16), C18(H18),
 C19(H19), C20(H20), C21(H21), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29),
  C30(H30), C31(H31)
2.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              32946
_shelx_hkl_checksum              27309
_olex2_submission_special_instructions 'No special instructions were received'