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_4130974
_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         'C37 H32 N4 O3'
_chemical_formula_sum            'C37 H32 N4 O3'
_chemical_formula_weight         580.66
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                84.356(3)
_cell_angle_beta                 85.371(3)
_cell_angle_gamma                79.193(4)
_cell_formula_units_Z            4
_cell_length_a                   8.8033(4)
_cell_length_b                   14.9971(7)
_cell_length_c                   24.8202(11)
_cell_measurement_reflns_used    5870
_cell_measurement_temperature    296
_cell_measurement_theta_max      65.68
_cell_measurement_theta_min      3.371
_cell_volume                     3196.6(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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296
_diffrn_measured_fraction_theta_full 0.942
_diffrn_measured_fraction_theta_max 0.942
_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  0.0536
_diffrn_reflns_av_unetI/netI     0.0935
_diffrn_reflns_Laue_measured_fraction_full 0.942
_diffrn_reflns_Laue_measured_fraction_max 0.942
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            23429
_diffrn_reflns_point_group_measured_fraction_full 0.641
_diffrn_reflns_point_group_measured_fraction_max 0.641
_diffrn_reflns_theta_full        66.350
_diffrn_reflns_theta_max         66.350
_diffrn_reflns_theta_min         3.011
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.620
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.5295
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1172 before and 0.0721 after correction.
The Ratio of minimum to maximum transmission is 0.7034.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.207
_exptl_crystal_description       pirsm
_exptl_crystal_F_000             1224
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.448
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.076
_refine_ls_abs_structure_details
;
 Flack x determined using 2376 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     1593
_refine_ls_number_reflns         14398
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0976
_refine_ls_R_factor_gt           0.0867
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1759P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2183
_refine_ls_wR_factor_ref         0.2413
_reflns_Friedel_coverage         0.361
_reflns_Friedel_fraction_full    0.340
_reflns_Friedel_fraction_max     0.340
_reflns_number_gt                11443
_reflns_number_total             14398
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b08236_si_004.cif
_cod_data_source_block           cu_dm16428_0m
_cod_database_code               4130974
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.913
_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. Uiso/Uaniso restraints and constraints
Uanis(C29) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C23B) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(O2A) \\sim Ueq, Uanis(O3C) \\sim Ueq, Uanis(O2C) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C35B) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(O3A) \\sim Ueq, Uanis(C13A)
\\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(O2C) \\sim Ueq, Uanis(O3C) \\sim Ueq:
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C29) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
3.a Ternary CH refined with riding coordinates:
 C5(H5), C5B(H5B), C5A(H5A), C5C(H5C)
3.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C31(H31A,H31B), C24B(H24C,H24D), C31B(H31C,H31D), C24A(H24E,
 H24F), C31A(H31E,H31F), C24C(H24G,H24H), C31C(H31G,H31H)
3.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C11(H11), C12(H12), C13(H13), C14(H14), C18(H18),
 C19(H19), C21(H21), C22(H22), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30),
  C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C6B(H6B), C7B(H7B),
 C8B(H8B), C11B(H11B), C12B(H12B), C13B(H13B), C14B(H14B), C18B(H18B),
 C19B(H19B), C21B(H21B), C22B(H22B), C26B(H26B), C27B(H27B), C28B(H28B),
 C29B(H29B), C30B(H30B), C33B(H33B), C34B(H34B), C35B(H35B), C36B(H36B),
 C37B(H37B), C6A(H6A), C7A(H7A), C8A(H8A), C11A(H11A), C12A(H12A), C13A(H13A),
 C14A(H14A), C18A(H18A), C19A(H19A), C21A(H21A), C22A(H22A), C26A(H26A),
 C27A(H27A), C28A(H28A), C29A(H29A), C30A(H30A), C33A(H33A), C34A(H34A),
 C35A(H35A), C36A(H36A), C37A(H37A), C6C(H6C), C7C(H7C), C8C(H8C), C11C(H11C),
 C12C(H12C), C13C(H13C), C14C(H14C), C18C(H18C), C19C(H19C), C21C(H21C),
 C22C(H22C), C26C(H26C), C27C(H27C), C28C(H28C), C29C(H29C), C30C(H30C),
 C33C(H33C), C34C(H34C), C35C(H35C), C36C(H36C), C37C(H37C)
3.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C23(H23A,H23B,H23C), C4B(H4BA,H4BB,H4BC), C23B(H23D,H23E,
 H23F), C4A(H4AA,H4AB,H4AC), C23A(H23G,H23H,H23I), C4C(H4CA,H4CB,H4CC),
 C23C(H23J,H23K,H23L)
;
_shelx_res_checksum              23624
_shelx_hkl_checksum              67875
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'