Chiral Primary Amine-Catalyzed Divergent Coupling of α-Substituted Acrylaldehydes with α-Diazoesters
Xue, Zaikun; Li, Yao; Luo, Sanzhong; ACS Catalysis  (2020) 10989–; doi:10.1021/acscatal.0c02405

data_4518039
_publ_section_title
;
 Chiral Primary Amine-Catalyzed Divergent Coupling of \a-Substituted
 Acrylaldehydes with \a-Diazoesters
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              10989
_journal_paper_doi               10.1021/acscatal.0c02405
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C27 H26 N4 O6'
_chemical_formula_sum            'C27 H26 N4 O6'
_chemical_formula_weight         502.52
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.0580(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.25553(3)
_cell_length_b                   7.40220(4)
_cell_length_c                   47.0222(2)
_cell_measurement_reflns_used    37781
_cell_measurement_temperature    170.00(13)
_cell_measurement_theta_max      75.2030
_cell_measurement_theta_min      2.8040
_cell_volume                     2523.79(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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_environment      N~2~
_diffrn_ambient_temperature      170.00(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.976
_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 -34.00   0.50    0.05    --  -47.20 -23.00-107.00  176
  2  \w    -26.00  27.00   0.50    0.05    --  -47.20  23.00  56.00  106
  3  \w     35.00 122.00   0.50    0.05    --   47.20  23.00  56.00  174
  4  \w    -27.00  33.00   0.50    0.05    --   47.20 -23.00-107.00  120
  5  \w   -168.00 -86.00   0.50    0.08    --  -99.00 -23.00-107.00  164
  6  \w     90.00 169.00   0.50    0.08    --  103.25  23.00  56.00  158
  7  \w    -39.00  26.00   0.50    0.05    --  -47.20  38.00-180.00  130
  8  \w     35.00 120.00   0.50    0.05    --   47.20  38.00 120.00  170
  9  \w     35.00 120.00   0.50    0.05    --   47.20  38.00-180.00  170
 10  \w     25.00 120.00   0.50    0.05    --   47.20  77.00-180.00  190
 11  \w     25.00 120.00   0.50    0.05    --   47.20  77.00 120.00  190
 12  \w   -168.00 -75.00   0.50    0.08    --  -99.00 -79.00-148.99  186
 13  \w   -168.00 -86.00   0.50    0.08    --  -99.00 -45.00 120.00  164
 14  \w   -150.00 -82.00   0.50    0.08    --  -99.00 -61.00-150.00  136
 15  \w   -165.00 -81.00   0.50    0.08    --  -99.00 -65.00 159.65  168
 16  \w   -166.00-140.00   0.50    0.08    --  -99.00 -77.00 129.93   52
 17  \w   -102.00 -76.00   0.50    0.08    --  -99.00 -76.00-136.79   52
 18  \w   -110.00 -77.00   0.50    0.08    --  -99.00 -75.00 146.49   66
 19  \w   -147.00-121.00   0.50    0.08    --  -99.00 -78.00-147.42   52
 20  \w   -109.00 -76.00   0.50    0.08    --  -99.00 -76.00 163.27   66
 21  \w   -168.00 -81.00   0.50    0.08    --  -99.00 -64.00-126.88  174
 22  \w   -148.00 -78.00   0.50    0.08    --  -99.00 -73.00-172.72  140
 23  \w   -104.00 -78.00   0.50    0.08    --  -99.00 -74.00 119.31   52
 24  \w   -168.00-142.00   0.50    0.08    --  -99.00 -76.00 163.27   52
 25  \w   -103.00 -77.00   0.50    0.08    --  -99.00 -77.00 120.00   52
 26  \w   -104.00 -76.00   0.50    0.08    --  -99.00 -77.00 129.93   56
 27  \w    -67.00 -26.00   0.50    0.08    --  -99.00  61.00 -60.00   82
 28  \w   -161.00 -81.00   0.50    0.08    --  -99.00 -67.00 104.16  160
 29  \w   -103.00 -77.00   0.50    0.08    --  -99.00 -75.00-162.15   52
 30  \w   -103.00 -77.00   0.50    0.08    --  -99.00 -74.00 130.05   52
 31  \w   -117.00 -75.00   0.50    0.08    --  -99.00 -79.00 113.54   84
 32  \w   -104.00 -78.00   0.50    0.08    --  -99.00 -77.00-180.00   52
 33  \w   -105.00 -79.00   0.50    0.08    --  -99.00 -71.00-165.09   52
 34  \w   -103.00 -77.00   0.50    0.08    --  -99.00 -77.00-120.00   52
 35  \w   -101.00 -76.00   0.50    0.08    --  -99.00 -76.00-161.79   50
 36  \w   -102.00 -76.00   0.50    0.08    --  -99.00 -78.00-147.42   52
 37  \w   -106.00 -80.00   0.50    0.08    --  -99.00 -67.00 133.87   52
 38  \w   -166.00 -79.00   0.50    0.08    --  -99.00 -70.00 179.11  174
 39  \w   -118.00 -85.00   0.50    0.08    --  -99.00 -55.00-168.86   66
 40  \w   -168.00 -82.00   0.50    0.08    --  -99.00 -61.00-145.76  172
 41  \w     49.00  75.00   0.50    0.08    --  103.25 -61.00 120.00   52
 42  \w     31.00  58.00   0.50    0.08    --  103.25 -94.00 150.00   54
 43  \w     75.00 105.00   0.50    0.08    --  103.25 -77.00  60.00   60
 44  \w     34.00  68.00   0.50    0.08    --  103.25 -77.00  60.00   68
 45  \w     31.00  56.00   0.50    0.08    --  103.25 -61.00  30.00   50
 46  \w     33.00  73.00   0.50    0.08    --  103.25 -61.00  60.00   80
 47  \w     31.00  81.00   0.50    0.08    --  103.25 -77.00 -60.00  100
 48  \w     31.00  74.00   0.50    0.08    --  103.25 -61.00 -30.00   86
 49  \w     40.00  66.00   0.50    0.08    --  103.25 -94.00  30.00   52
 50  \w     32.00  69.00   0.50    0.08    --  103.25 -61.00-180.00   74
 51  \w     68.00 106.00   0.50    0.08    --  103.25 -94.00 150.00   76
 52  \w     31.00  75.00   0.50    0.08    --  103.25 -61.00 -60.00   88
 53  \w     33.00  73.00   0.50    0.08    --  103.25 -61.00 150.00   80
 54  \w     33.00  59.00   0.50    0.08    --  103.25 -61.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0642597000
_diffrn_orient_matrix_UB_12      -0.0566403000
_diffrn_orient_matrix_UB_13      0.0302865000
_diffrn_orient_matrix_UB_21      0.2023116000
_diffrn_orient_matrix_UB_22      0.0273477000
_diffrn_orient_matrix_UB_23      -0.0079224000
_diffrn_orient_matrix_UB_31      -0.0095097000
_diffrn_orient_matrix_UB_32      0.1983649000
_diffrn_orient_matrix_UB_33      0.0097367000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       58
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            48243
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.453
_diffrn_reflns_theta_min         2.821
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.786
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60332
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       plate
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.570
_refine_diff_density_min         -0.283
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 4120 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     779
_refine_ls_number_reflns         9822
_refine_ls_number_restraints     146
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0354
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0570P)^2^+0.4754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0929
_refine_ls_wR_factor_ref         0.0935
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    0.958
_reflns_Friedel_fraction_max     0.900
_reflns_number_gt                9599
_reflns_number_total             9822
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02405_si_002.cif
_cod_data_source_block           tx2552
_cod_original_cell_volume        2523.78(2)
_cod_database_code               4518039
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNO
_chemical_oxdiff_usercomment     CHON
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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. Rigid bond restraints
 C1A, C2A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
3. Uiso/Uaniso restraints and constraints
Uanis(C6A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C9A)
\\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C11C) \\sim Ueq,
Uanis(C10C) \\sim Ueq, Uanis(C8C) \\sim Ueq, Uanis(C9C) \\sim Ueq, Uanis(C6C)
\\sim Ueq, Uanis(C7C) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim
Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C8B) \\sim Ueq,
Uanis(C7B) \\sim Ueq, Uanis(C11B) \\sim Ueq, Uanis(C9B) \\sim Ueq, Uanis(C6B)
\\sim Ueq, Uanis(C10B) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Others
 Sof(H5AE)=Sof(H5AF)=Sof(C6C)=Sof(C7C)=Sof(H7C)=Sof(C8C)=Sof(H8C)=Sof(C9C)=
 Sof(H9C)=Sof(C10C)=Sof(H10C)=Sof(C11C)=Sof(H11C)=1-FVAR(1)
 Sof(H5AC)=Sof(H5AD)=Sof(C6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=
 Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=FVAR(1)
 Sof(H5BC)=Sof(H5BD)=Sof(C6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=Sof(C9B)=
 Sof(H9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=1-FVAR(2)
 Sof(H5AA)=Sof(H5AB)=Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C1A(H1A)
5.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5AA,H5AB), C5(H5BC,H5BD), C14(H14A,H14B), C3A(H3AA,H3AB),
 C5A(H5AC,H5AD), C5A(H5AE,H5AF), C14A(H14C,H14D)
5.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C7(H7), C7B(H7B), C8(H8), C8B(H8B), C9(H9), C9B(H9B), C10(H10),
 C10B(H10B), C11(H11), C11B(H11B), C12(H12), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C23(H23), C24(H24), C26(H26), N2A(H2A), C7A(H7A),
  C7C(H7C), C8A(H8A), C8C(H8C), C9A(H9A), C9C(H9C), C10A(H10A), C10C(H10C),
 C11A(H11A), C11C(H11C), C12A(H12A), C16A(H16A), C17A(H17A), C18A(H18A),
 C19A(H19A), C20A(H20A), C21A(H21A), C23A(H23A), C24A(H24A), C26A(H26A)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C4A(H4AA,H4AB,H4AC)
;
_shelx_res_checksum              10797
_shelx_hkl_checksum              93642
_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 1.590
_oxdiff_exptl_absorpt_empirical_full_min 0.701