Palladium Catalyzed C-H Glycosylation and Retro Diels-Alder Tandem Reaction via Structurally Modified Norbornadiene (smNBDs)
An, Yang; Zhang, Bo-Sheng; Ding, Ya-Nan; Zhang, Zhe; Gou, Xue-Ya; Li, Xue-Song; Wang, Xiaolei; Li, Yuke; Liang, Yong-Min; Chemical Science  (2021) –; doi:10.1039/D1SC03569J

data_1564495
_publ_section_title
;
 Palladium Catalyzed C-H Glycosylation and Retro Diels-Alder Tandem
 Reaction via Structurally Modified Norbornadiene (smNBDs)
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC03569J
_journal_year                    2021
_chemical_formula_moiety         'C60 H57 N O2 P2 Pd S, C H2 Cl2'
_chemical_formula_sum            'C61 H59 Cl2 N O2 P2 Pd S'
_chemical_formula_weight         1109.39
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-12-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-03-04 deposited with the CCDC.	2021-08-31 downloaded from the CCDC.
;
_cell_angle_alpha                70.689(3)
_cell_angle_beta                 89.007(2)
_cell_angle_gamma                77.468(2)
_cell_formula_units_Z            2
_cell_length_a                   11.5489(3)
_cell_length_b                   13.5596(5)
_cell_length_c                   18.1117(6)
_cell_measurement_reflns_used    10412
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      75.8580
_cell_measurement_theta_min      2.5840
_cell_volume                     2608.35(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.959
_diffrn_measured_fraction_theta_max 0.894
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -36.00  21.00   1.00    2.00    --   43.05 -19.00  30.00   57
  2  \w     -9.00  40.00   1.00    2.00    --   43.05 -37.00 120.00   49
  3  \w      5.00  32.00   1.00    2.00    --   43.05-109.00  19.00   27
  4  \w    -37.00  23.00   1.00    2.00    --   43.05 -19.00 -90.00   60
  5  \w     34.00  75.00   1.00    2.00    --   43.05 -99.00-180.00   41
  6  \w     36.00 111.00   1.00    8.00    --  109.26-125.00-150.00   75
  7  \w     41.00 103.00   1.00    8.00    --  109.26 -77.00-180.00   62
  8  \w     35.00 100.00   1.00    8.00    --  109.26 -77.00 -30.00   65
  9  \w     68.00 104.00   1.00    8.00    --  109.26 -94.00  60.00   36
 10  \w     73.00 100.00   1.00    8.00    --  109.26 -94.00 120.00   27
 11  \w     70.00 111.00   1.00    8.00    --  109.26-125.00  90.00   41
 12  \w     42.00  69.00   1.00    8.00    --  109.26 -61.00  30.00   27
 13  \w     37.00  69.00   1.00    8.00    --  109.26 -61.00  90.00   32
 14  \w     36.00  64.00   1.00    8.00    --  109.26 -94.00  60.00   28
 15  \w     38.00  64.00   1.00    8.00    --  109.26-125.00  90.00   26
 16  \w     46.00  72.00   1.00    8.00    --  109.26-109.00  19.00   26
 17  \w    -34.00  33.00   1.00    2.00    --   43.05 -37.00-180.00   67
 18  \w      2.00  29.00   1.00    2.00    --   43.05 -99.00-180.00   27
 19  \w    -34.00  37.00   1.00    2.00    --   43.05 -37.00 -90.00   71
 20  \w     84.00 152.00   1.00    8.00    --  109.26 109.00 115.00   68
 21  \w    -54.00 -24.00   1.00    8.00    -- -100.00  45.00-150.00   30
 22  \w    -59.00 -27.00   1.00    8.00    -- -100.00  77.00-150.00   32
 23  \w    -61.00 -34.00   1.00    8.00    -- -100.00 108.00-124.41   27
 24  \w    -76.00 -26.00   1.00    8.00    -- -100.00 125.00 -90.00   50
 25  \w    -54.00 -28.00   1.00    8.00    -- -100.00  45.00  60.00   26
 26  \w    -52.00 -25.00   1.00    8.00    -- -100.00  45.00  90.00   27
 27  \w    -74.00 -48.00   1.00    2.00    --  -43.05 109.00 115.00   26
 28  \w   -125.00 -90.00   1.00    8.00    -- -100.00-109.00  19.00   35
 29  \w   -121.00 -82.00   1.00    8.00    -- -100.00-125.00 -30.00   39
 30  \w   -120.00 -49.00   1.00    2.00    --  -43.05-179.00 -60.00   71
 31  \w   -120.00 -93.00   1.00    8.00    -- -100.00-125.00 120.00   27
 32  \w   -157.00-129.00   1.00    8.00    -- -100.00-109.00  19.00   28
 33  \w   -152.00-125.00   1.00    8.00    -- -100.00-125.00 -30.00   27
 34  \w   -156.00-125.00   1.00    8.00    -- -100.00 -61.00-120.00   31
 35  \w   -149.00-122.00   1.00    8.00    -- -100.00 -94.00-180.00   27
 36  \w   -176.00 -76.00   1.00    8.00    -- -100.00 -30.00-150.00  100
 37  \w   -108.00 -82.00   1.00    8.00    -- -100.00  77.00-150.00   26
 38  \w   -107.00 -64.00   1.00    8.00    -- -100.00 108.00-124.41   43
 39  \w   -109.00 -81.00   1.00    8.00    -- -100.00 125.00 -90.00   28
 40  \w   -112.00 -87.00   1.00    8.00    -- -100.00 125.00 -30.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0407337000
_diffrn_orient_matrix_UB_12      0.0786307000
_diffrn_orient_matrix_UB_13      0.0332629000
_diffrn_orient_matrix_UB_21      0.0233081000
_diffrn_orient_matrix_UB_22      -0.0871130000
_diffrn_orient_matrix_UB_23      0.0816047000
_diffrn_orient_matrix_UB_31      0.1285926000
_diffrn_orient_matrix_UB_32      -0.0385556000
_diffrn_orient_matrix_UB_33      -0.0196493000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0526
_diffrn_reflns_av_unetI/netI     0.0616
_diffrn_reflns_Laue_measured_fraction_full 0.959
_diffrn_reflns_Laue_measured_fraction_max 0.894
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25457
_diffrn_reflns_point_group_measured_fraction_full 0.959
_diffrn_reflns_point_group_measured_fraction_max 0.894
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.057
_diffrn_reflns_theta_min         2.590
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.115
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65397
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.413
_exptl_crystal_description       plate
_exptl_crystal_F_000             1148
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.724
_refine_diff_density_min         -0.909
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     644
_refine_ls_number_reflns         9750
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0523
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0453P)^2^+1.7827P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0960
_refine_ls_wR_factor_ref         0.1002
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8373
_reflns_number_total             9750
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc03569j2.cif
_cod_data_source_block           anyang_1223_2
_cod_original_cell_volume        2608.35(15)
_cod_database_code               1564495
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.579
_reflns_odcompleteness_completeness 96.04
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: HD(0.4) HE(0.4) H01(0.6) HF(0.6) Cl1(0.4) Cl27(0.6)
3.a Ternary CH refined with riding coordinates:
 C00J(H00J), C00K(H00K), C00V(H00V), C010(H010)
3.b Secondary CH2 refined with riding coordinates:
 C00U(H00A,H00C), C01Y(HD,HE), C01Y(H01,HF)
3.c Aromatic/amide H refined with riding coordinates:
 N009(H009), C00B(H00B), C00E(H00E), C00F(H00F), C00L(H00L), C00M(H00M),
 C00N(H00N), C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S),
 C00T(H00T), C00W(H00W), C00Y(H00Y), C00Z(H00Z), C011(H011), C014(H014),
 C016(H016), C017(H017), C018(H018), C01A(H01A), C01B(H01B), C01C(H01C),
 C01D(H01D), C01E(H01E), C01F(H01F), C01G(H01G), C01H(H01H), C01J(H01J),
 C01K(H01K), C01L(H01L), C01N(H01N), C01O(H01O), C01P(H01P), C01Q(H01Q),
 C01R(H01R), C01S(H01S), C01U(H01U)
3.d Idealised Me refined as rotating group:
 C01T(H01I,H01M,H01T), C01V(H01V,H01W,H01X), C01W(H01Y,H,HA), C01X(H01Z,HB,HC)
;
_shelx_res_checksum              55051
_shelx_hkl_checksum              88373
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.368
_oxdiff_exptl_absorpt_empirical_full_min 0.754