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_4130973
_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         'C30 H25 Cl N4 O3'
_chemical_formula_sum            'C30 H25 Cl N4 O3'
_chemical_formula_weight         524.99
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-08
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 118.307(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   29.178(6)
_cell_length_b                   7.2062(14)
_cell_length_c                   27.810(6)
_cell_measurement_reflns_used    2779
_cell_measurement_temperature    130
_cell_measurement_theta_max      25.460
_cell_measurement_theta_min      2.797
_cell_volume                     5148.2(18)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0635
_diffrn_reflns_av_unetI/netI     0.1089
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            21413
_diffrn_reflns_point_group_measured_fraction_full 0.932
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.600
_diffrn_reflns_theta_min         0.832
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.189
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6666
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0979 before and 0.0514 after correction.
The Ratio of minimum to maximum transmission is 0.8940.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       block
_exptl_crystal_F_000             2192
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.245
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 2129 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.07(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.970
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     689
_refine_ls_number_reflns         11058
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.970
_refine_ls_R_factor_all          0.1089
_refine_ls_R_factor_gt           0.0561
_refine_ls_shift/su_max          0.016
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0308P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0840
_refine_ls_wR_factor_ref         0.0994
_reflns_Friedel_coverage         0.718
_reflns_Friedel_fraction_full    0.852
_reflns_Friedel_fraction_max     0.839
_reflns_number_gt                6946
_reflns_number_total             11058
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b08236_si_003.cif
_cod_data_source_block           mo_dm16427_0m
_cod_original_cell_volume        5148.3(18)
_cod_database_code               4130973
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.963
_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:
 C2(H2A,H2B), C9(H9A,H9B), C32(H32A,H32B), C39(H39A,H39B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C14(H14), C15(H15), C17(H17),
 C18(H18), C20(H20), C21(H21), C25(H25), C26(H26), C27(H27), C28(H28), C33(H33),
  C34(H34), C35(H35), C41(H41), C42(H42), C44(H44), C45(H45), C47(H47),
 C48(H48), C50(H50), C51(H51), C55(H55), C56(H56), C57(H57), C58(H58)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C22(H22A,H22B,H22C), C38(H38A,H38B,H38C), C52(H52A,H52B,H52C)
;
_shelx_res_checksum              99673
_shelx_hkl_checksum              24936
_olex2_submission_special_instructions 'No special instructions were received'