π-Coordinating Chiral Primary Amine/Palladium Synergistic Catalysis for Asymmetric Allylic Alkylation.
Wang, Yaning; Chai, Junli; You, Chang; Zhang, Jie; Mi, Xueling; Zhang, Long; Luo, Sanzhong; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b13026

data_4134089
_publ_section_title
;
 \p-Coordinating Chiral Primary Amine/Palladium Synergistic Catalysis for
 Asymmetric Allylic Alkylation.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b13026
_journal_year                    2020
_chemical_formula_moiety
'C3 H5 Cl2 Pd, C F3 O3 S, C18 H26 N2, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C22.5 H32 Cl3 F3 N2 O3 Pd S'
_chemical_formula_weight         680.25
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
????
;
_cell_angle_alpha                87.77(3)
_cell_angle_beta                 85.00(3)
_cell_angle_gamma                86.84(3)
_cell_formula_units_Z            2
_cell_length_a                   7.3867(15)
_cell_length_b                   12.145(2)
_cell_length_c                   15.767(3)
_cell_measurement_reflns_used    5149
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.4819
_cell_measurement_theta_min      1.2972
_cell_volume                     1406.1(5)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2014)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'MM007-HF CCD(Saturn 724+)'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            19059
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         2.087
_diffrn_source                   'Rotating Anode'
_exptl_absorpt_coefficient_mu    1.066
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83029
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_diffrn    1.607
_exptl_crystal_description       block
_exptl_crystal_F_000             690
_exptl_crystal_size_max          0.303
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.19
_refine_diff_density_max         1.155
_refine_diff_density_min         -0.677
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.162
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     457
_refine_ls_number_reflns         6390
_refine_ls_number_restraints     249
_refine_ls_restrained_S_all      1.159
_refine_ls_R_factor_all          0.0618
_refine_ls_R_factor_gt           0.0595
_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^)+8.0679P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1327
_refine_ls_wR_factor_ref         0.1353
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6194
_reflns_number_total             6390
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b13026_si_003.cif
_cod_data_source_block           mx7081
_cod_original_cell_volume        1406.2(5)
_cod_original_formula_sum        'C22.50 H32 Cl3 F3 N2 O3 Pd S'
_cod_database_code               4134089
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.823
_shelx_estimated_absorpt_t_min   0.738
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl3-C23 = Cl4-C23
 1.76 with sigma of 0.01
 S1A-O1A = S1A-O2A = S1A-O3A
 1.43 with sigma of 0.01
 F2A-C22A = F1A-C22A = F3A-C22A
 1.34 with sigma of 0.01
 C9-C10 = C9-C10A = C11A-C1 = C11-C1 = C11A-N11A = N11A-C10A = C11-N1
 1.51 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl3 \\sim Cl4 \\sim C23: within 1.9A with sigma of 0.02 and sigma for terminal
atoms of 0.04
F2A \\sim S1A \\sim O1A \\sim O2A \\sim O3A \\sim C22A \\sim F1A \\sim F3A:
within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
N1 \\sim C10 \\sim C11 \\sim C13 \\sim C14 \\sim C10A \\sim C11A \\sim N11A
\\sim C13A \\sim C14A: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(Cl3) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(Cl4) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C10) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C10A) \\sim Ueq,
Uanis(C11A) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(N11A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H2BD)=Sof(H2BE)=Sof(H2BF)=Sof(C10A)=Sof(H10C)=Sof(H10D)=Sof(C11A)=
 Sof(H11C)=Sof(H11D)=Sof(N11A)=Sof(H11E)=Sof(C13A)=Sof(H13C)=Sof(H13D)=
 Sof(C14A)=Sof(H14A)=1-FVAR(1)
 Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(N1)=Sof(H1)=Sof(C10)=Sof(H10A)=Sof(H10B)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14)=
 FVAR(1)
 Sof(S1A)=Sof(C22A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(F2A)=Sof(F1A)=Sof(F3A)=1-
 FVAR(2)
 Sof(F1)=Sof(O1)=Sof(S1)=Sof(F2)=Sof(O2)=Sof(F3)=Sof(O3)=Sof(C22)=FVAR(2)
 Fixed Sof: Cl3(0.5) Cl4(0.5) C23(0.5) H23A(0.5) H23B(0.5)
5.a Riding coordinates:
 C20(H20), C21(H21A,H21B)
5.b Ternary CH refined with riding coordinates:
 N1(H1), C14(H14), N11A(H11E), C14A(H14A)
5.c Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C10A(H10C,
 H10D), C11A(H11C,H11D), C13A(H13C,H13D), C23(H23A,H23B)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C6(H6), C7(H7), C8(H8)
5.e Idealised Me refined as rotating group:
 N2(H2AA,H2AB,H2AC), N2(H2BD,H2BE,H2BF), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              62940
_shelx_hkl_checksum              71141
_olex2_submission_special_instructions 'No special instructions were received'