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_1564496
_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_absolute_configuration ad
_chemical_formula_moiety         'C25 H35 N O5'
_chemical_formula_sum            'C25 H35 N O5'
_chemical_formula_weight         429.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2020-12-03 deposited with the CCDC.	2021-08-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.360(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.0067(3)
_cell_length_b                   9.2663(2)
_cell_length_c                   24.1638(8)
_cell_measurement_reflns_used    3140
_cell_measurement_temperature    293.77(10)
_cell_measurement_theta_max      69.2790
_cell_measurement_theta_min      4.7210
_cell_volume                     2431.69(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.77(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    122.00 177.00   1.00    2.00    --  108.00  77.00  90.00   55
  2  \w     87.00 166.00   1.00    2.00    --  108.00  63.00   0.00   79
  3  \w     90.00 174.00   1.00    2.00    --  108.00  63.00 120.00   84
  4  \w     89.00 137.00   1.00    2.00    --  108.00  63.00 150.00   48
  5  \w     78.00 171.00   1.00    2.00    --  108.00  77.00  30.00   93
  6  \w     70.00  96.00   1.00    2.00    --  108.00 -63.00 -90.00   26
  7  \w     65.00  93.00   1.00    2.00    --   54.00-125.00-150.00   28
  8  \w     47.00 131.00   1.00    2.00    --  108.00 -77.00 -90.00   84
  9  \w     34.00 123.00   1.00    2.00    --   54.00  57.00  30.00   89
 10  \w     37.00  77.00   1.00    2.00    --  108.00-111.00 -90.00   40
 11  \w     -4.00  83.00   1.00    2.00    --   54.00 -77.00-120.00   87
 12  \w    -22.00  11.00   1.00    1.00    --    0.00 -57.00-180.00   33
 13  \w    -68.00 -36.00   1.00    1.00    --    0.00 -57.00-180.00   32
 14  \w    -47.00 -21.00   1.00    1.00    --    0.00 110.00 -70.00   26
 15  \w     -3.00  75.00   1.00    2.00    --   54.00 -57.00 120.00   78
 16  \w     26.00  58.00   1.00    1.00    --    0.00  57.00-150.00   32
 17  \w    -23.00   3.00   1.00    1.00    --    0.00  91.00  34.00   26
 18  \w    -19.00  16.00   1.00    1.00    --    0.00  57.00-150.00   35
 19  \w     46.00  93.00   1.00    2.00    --   54.00  57.00-120.00   47
 20  \w     39.00 122.00   1.00    2.00    --   54.00  57.00 120.00   83
 21  \w     43.00  68.00   1.00    2.00    --   54.00  57.00-180.00   25
 22  \w    -14.00  62.00   1.00    2.00    --   54.00 -57.00 -30.00   76
 23  \w     78.00 178.00   1.00    2.00    --  108.00  77.00 -30.00  100
 24  \w    101.00 147.00   1.00    2.00    --  108.00 111.00  60.00   46
 25  \w    121.00 146.00   1.00    2.00    --  108.00 111.00 150.00   25
 26  \w    100.00 150.00   1.00    2.00    --  108.00  63.00 -60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0267890000
_diffrn_orient_matrix_UB_12      -0.1403850000
_diffrn_orient_matrix_UB_13      -0.0298746000
_diffrn_orient_matrix_UB_21      -0.0721569000
_diffrn_orient_matrix_UB_22      0.0584882000
_diffrn_orient_matrix_UB_23      -0.0554971000
_diffrn_orient_matrix_UB_31      0.1191130000
_diffrn_orient_matrix_UB_32      0.0670524000
_diffrn_orient_matrix_UB_33      -0.0143916000
_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  0.0187
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            7101
_diffrn_reflns_point_group_measured_fraction_full 0.910
_diffrn_reflns_point_group_measured_fraction_max 0.910
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.601
_diffrn_reflns_theta_min         4.190
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.652
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33627
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.173
_exptl_crystal_description       block
_exptl_crystal_F_000             928
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.148
_refine_diff_density_min         -0.160
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1301 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     324
_refine_ls_number_reflns         3898
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0478
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0578P)^2^+0.4891P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1115
_reflns_Friedel_coverage         0.707
_reflns_Friedel_fraction_full    0.808
_reflns_Friedel_fraction_max     0.808
_reflns_number_gt                3513
_reflns_number_total             3898
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc03569j2.cif
_cod_data_source_block           anyang_0921_3
_cod_original_cell_volume        2431.67(13)
_cod_database_code               1564496
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.87
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O5) \\sim Ueq, Uanis(O007) \\sim Ueq, Uanis(O19) \\sim Ueq, Uanis(O00M)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: O007(0.5) H00H(0.5) H00E(0.5) O00M(0.5) H00O(0.5) H00P(0.5)
 H00M(0.5) H00N(0.5) O19(0.5) C3(0.5) H3A(0.5) H3B(0.5) H3C(0.5) C4(0.5)
 H4A(0.5) H4B(0.5) H4C(0.5) C3AA(0.5) H3AA(0.5) H3AB(0.5) H3AC(0.5) C4AA(0.5)
 H4AA(0.5) H4AB(0.5) H4AC(0.5) O5(0.5)
4.a Ternary CH refined with riding coordinates:
 C009(H009), C00C(H00C), C00D(H00D), C00G(H00G), C00H(H00H), C00H(H00E),
 C00O(H00Q)
4.b Secondary CH2 refined with riding coordinates:
 C00N(H00O,H00P), C00N(H00M,H00N), C1(H1A,H1B), C2(H2A,H2B)
4.c Aromatic/amide H refined with riding coordinates:
 C006(H006), C00A(H00A), C00B(H00B), C00F(H00F), C00I(H00I)
4.d Idealised Me refined as rotating group:
 C00L(H00J,H00K,H00L), C0AA(H0AA,H0AB,H0AC), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C),
 C1AA(H1AA,H1AB,H1AC), C2AA(H2AA,H2AB,H2AC), C3AA(H3AA,H3AB,H3AC), C4AA(H4AA,
 H4AB,H4AC)
;
_shelx_res_checksum              66858
_shelx_hkl_checksum              78464
_olex2_date_sample_data_collection 2020-09-21
_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 2.529
_oxdiff_exptl_absorpt_empirical_full_min 0.594