Stereoselective alkoxycarbonylation of unactivated C(sp3)-H bonds with alkyl chloroformates via Pd(II)/Pd(IV) catalysis
Gang Liao; Xue-Song Yin; Kai Chen; Qi Zhang; Shuo-Qing Zhang; Bing-Feng Shi; Nature Communications 7 (2016) 12901–; doi:10.1038/ncomms12901

data_1548364
_publ_section_title
;
 Stereoselective alkoxycarbonylation of unactivated C(sp3)-H bonds with
 alkyl chloroformates via Pd(II)/Pd(IV) catalysis
;
_journal_name_full               'Nature Communications'
_journal_page_first              12901
_journal_paper_doi               10.1038/ncomms12901
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety         'C31 H21 N4 O3 Pd'
_chemical_formula_sum            'C31 H21 N4 O3 Pd'
_chemical_formula_weight         603.92
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                76.453(3)
_cell_angle_beta                 73.120(3)
_cell_angle_gamma                67.988(3)
_cell_formula_units_Z            2
_cell_length_a                   9.7625(4)
_cell_length_b                   10.5921(3)
_cell_length_c                   14.2369(5)
_cell_measurement_reflns_used    6969
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.5938
_cell_measurement_theta_min      3.0245
_cell_volume                     1292.94(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293.15
_diffrn_detector_area_resol_mean 10.3592
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0203219000
_diffrn_orient_matrix_UB_12      -0.0218582000
_diffrn_orient_matrix_UB_13      -0.0470710000
_diffrn_orient_matrix_UB_21      -0.0778101000
_diffrn_orient_matrix_UB_22      0.0183499000
_diffrn_orient_matrix_UB_23      0.0002069000
_diffrn_orient_matrix_UB_31      -0.0009398000
_diffrn_orient_matrix_UB_32      0.0671497000
_diffrn_orient_matrix_UB_33      -0.0234577000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            17400
_diffrn_reflns_theta_full        25.35
_diffrn_reflns_theta_max         25.35
_diffrn_reflns_theta_min         3.03
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.759
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93909
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.551
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             610
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.593
_refine_diff_density_min         -0.672
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.194
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     362
_refine_ls_number_reflns         4708
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.201
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0508
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+5.2840P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1118
_refine_ls_wR_factor_ref         0.1143
_reflns_number_gt                4280
_reflns_number_total             4708
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ncomms12901-s2.cif
_cod_data_source_block           151008_lg4_32
_cod_original_cell_volume        1292.94(8)
_cod_database_code               1548364
_chemical_oxdiff_formula         'Pd2 C30 H20 N8 O10'
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 N3-C11A
 1.5 with sigma of 0.02
 C11A-C12
 1.5 with sigma of 0.02
 C11-C12
 1.5 with sigma of 0.02
 C11-N3
 1.5 with sigma of 0.02
3. Others
 Sof(C11A)=Sof(H11A)=1-FVAR(1)
 Sof(C11)=Sof(H11)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C11(H11), C11A(H11A)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C7(H7), C8(H8), C9(H9), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C29(H29), C30(H30), C31(H31)
;