Construction of polycyclic structures with vicinal all-carbon quaternary stereocenters <i>via</i> an enantioselective photoenolization/Diels-Alder reaction.
Hou, Min; Xu, Mengmeng; Yang, Baochao; He, Haibing; Gao, Shuanhu; Chemical science 12 (2021) 7575–7582; doi:10.1039/d1sc00883h

data_1562177
_publ_section_title
;
 Construction of polycyclic structures with vicinal all-carbon quaternary
 stereocenters <i>via</i> an enantioselective photoenolization/Diels-Alder
 reaction.
;
_journal_issue                   21
_journal_name_full               'Chemical science'
_journal_page_first              7575
_journal_page_last               7582
_journal_paper_doi               10.1039/d1sc00883h
_journal_volume                  12
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C23 H26 O4)'
_chemical_formula_sum            'C46 H52 O8'
_chemical_formula_weight         732.87
_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             2019-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-15 deposited with the CCDC.	2021-04-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.5070(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.30660(10)
_cell_length_b                   8.37820(10)
_cell_length_c                   20.2485(2)
_cell_measurement_reflns_used    25611
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.3320
_cell_measurement_theta_min      3.9190
_cell_volume                     1905.76(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_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    -40.00  -9.00   1.00    1.00    --    0.00 -77.00  90.00   31
  2  \w    -27.00  -1.00   1.00    1.00    --    0.00 -57.00 150.00   26
  3  \w     44.00  83.00   1.00    1.00    --    0.00  38.00  30.00   39
  4  \w    -18.00  86.00   1.00    1.00    --    0.00  38.00  90.00  104
  5  \w    -31.00  21.00   1.00    1.00    --    0.00  82.00 150.00   52
  6  \w     42.00  89.00   1.00    1.00    --    0.00  38.00-180.00   47
  7  \w    -89.00 -42.00   1.00    1.00    --    0.00 -57.00 150.00   47
  8  \w    -19.00  39.00   1.00    1.00    --    0.00  38.00  30.00   58
  9  \w    -87.00 -46.00   1.00    1.00    --    0.00 -77.00  90.00   41
 10  \w      4.00  33.00   1.00    1.00    --    0.00  38.00-180.00   29
 11  \w     40.00  66.00   1.00    1.00    --    0.00  57.00-150.00   26
 12  \w    -23.00  33.00   1.00    1.00    --    0.00  57.00-150.00   56
 13  \w    -19.00  49.00   1.00    1.00    --    0.00  38.00 -60.00   68
 14  \w     71.00  96.00   1.00    1.00    --   95.80  61.00-150.00   25
 15  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  43.13   25
 16  \w    144.00 182.00   1.00    1.00    --   95.80  57.00 165.99   38
 17  \w     66.00  92.00   1.00    1.00    --   95.80  76.00 -38.39   26
 18  \w    130.00 161.00   1.00    1.00    --   95.80  73.00 -93.04   31
 19  \w     73.00 106.00   1.00    1.00    --   95.80  57.00 165.99   33
 20  \w     67.00 103.00   1.00    1.00    --   95.80  72.00  -1.93   36
 21  \w     63.00  90.00   1.00    1.00    --   95.80  82.00-120.00   27
 22  \w     83.00 124.00   1.00    1.00    --   95.80 -82.00-120.00   41
 23  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 24  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-180.00   25
 25  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 26  \w     70.00 183.00   1.00    1.00    --   95.80  62.00 102.17  113
 27  \w     63.00  91.00   1.00    1.00    --   95.80  82.00 150.00   28
 28  \w    121.00 184.00   1.00    1.00    --   95.80  82.00 150.00   63
 29  \w     10.00  42.00   1.00    1.00    --   95.80 -61.00  60.00   32
 30  \w     46.00 118.00   1.00    1.00    --   95.80 -61.00  60.00   72
 31  \w     67.00 123.00   1.00    1.00    --   95.80  73.00 -93.04   56
 32  \w      8.00  79.00   1.00    1.00    --   95.80 -82.00-120.00   71
 33  \w     77.00 185.00   1.00    1.00    --   95.80  45.00-120.00  108
 34  \w     68.00  93.00   1.00    1.00    --   95.80  70.00 -61.78   25
 35  \w     69.00 174.00   1.00    1.00    --   95.80  66.00-114.09  105
 36  \w     77.00 182.00   1.00    1.00    --   95.80  45.00  90.00  105
 37  \w     75.00 102.00   1.00    1.00    --   95.80  45.00-150.00   27
 38  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  60.00   26
 39  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  60.00   26
 40  \w     71.00 128.00   1.00    1.00    --   95.80  61.00   0.00   57
 41  \w    133.00 158.00   1.00    1.00    --   95.80  61.00   0.00   25
 42  \w     71.00  97.00   1.00    1.00    --   95.80  61.00  60.00   26
 43  \w     72.00  98.00   1.00    1.00    --   95.80  61.00 150.00   26
 44  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-150.00   26
 45  \w     66.00  92.00   1.00    1.00    --   95.80  77.00 -90.00   26
 46  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  90.00   26
 47  \w     63.00  89.00   1.00    1.00    --   95.80  82.00   0.00   26
 48  \w    110.00 135.00   1.00    1.00    --   95.80  82.00   0.00   25
 49  \w     75.00 185.00   1.00    1.00    --   95.80  45.00  60.00  110
 50  \w     72.00 185.00   1.00    1.00    --   95.80  61.00 -30.00  113
 51  \w     65.00  91.00   1.00    1.00    --   95.80  77.00   0.00   26
 52  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 53  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 54  \w     71.00 185.00   1.00    1.00    --   95.80  61.00 -60.00  114
 55  \w     41.00 126.00   1.00    1.00    --   95.80 -82.00-150.00   85
 56  \w     65.00 127.00   1.00    1.00    --   95.80 -82.00   0.00   62
 57  \w     59.00 120.00   1.00    1.00    --   95.80 -82.00  90.00   61
 58  \w    135.00 161.00   1.00    1.00    --   95.80  76.00 -42.73   26
 59  \w     76.00 112.00   1.00    1.00    --   95.80  30.00-150.00   36
 60  \w    119.00 144.00   1.00    1.00    --   95.80  77.00 -60.00   25
 61  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 62  \w     11.00  95.00   1.00    1.00    --   95.80 -82.00  60.00   84
 63  \w     45.00  72.00   1.00    1.00    --   95.80 -82.00 -90.00   27
 64  \w     65.00  91.00   1.00    1.00    --   95.80  76.00 -42.73   26
 65  \w    133.00 158.00   1.00    1.00    --   95.80  72.00  -1.93   25
 66  \w    125.00 185.00   1.00    1.00    --   95.80  66.00 129.88   60
 67  \w     95.00 126.00   1.00    1.00    --   95.80 -82.00 -90.00   31
 68  \w     69.00  95.00   1.00    1.00    --   95.80  66.00 129.88   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0792907000
_diffrn_orient_matrix_UB_12      -0.0743334000
_diffrn_orient_matrix_UB_13      -0.0488923000
_diffrn_orient_matrix_UB_21      -0.1115421000
_diffrn_orient_matrix_UB_22      -0.0398036000
_diffrn_orient_matrix_UB_23      -0.0481183000
_diffrn_orient_matrix_UB_31      0.0088957000
_diffrn_orient_matrix_UB_32      0.1634705000
_diffrn_orient_matrix_UB_33      -0.0339670000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1011
_diffrn_reflns_av_unetI/netI     0.0502
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            45553
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.532
_diffrn_reflns_theta_min         3.935
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.693
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33227
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.449
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 3150 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(11)
_refine_ls_extinction_coef       0.0039(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     503
_refine_ls_number_reflns         7638
_refine_ls_number_restraints     184
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0542
_refine_ls_R_factor_gt           0.0527
_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^)+(0.0610P)^2^+1.0425P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1328
_refine_ls_wR_factor_ref         0.1344
_reflns_Friedel_coverage         0.834
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                7341
_reflns_number_total             7638
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00883h2.cif
_cod_data_source_block           exp_680
_cod_depositor_comments
'Adding full bibliography for 1562171--1562180.cif.'
_cod_database_code               1562177
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.840
_shelx_estimated_absorpt_t_min   0.741
_reflns_odcompleteness_completeness 99.97
_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, All O(H) groups
2. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
C3 \\sim C4: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
C12 \\sim C11: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
Uanis(C11) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C4) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4. Others
 Fixed Sof: H10A(0.5) H10B(0.5) H10C(0.5) H10D(0.5) C11A(0.5) H11A(0.5)
 H11B(0.5) C11(0.5) H11C(0.5) H11D(0.5)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C14(H14), C31(H31), C37(H37)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B), C10(H10C,H10D), C17(H17A,H17B),
 C11A(H11A,H11B), C11(H11C,H11D), C30(H30A,H30B), C32(H32A,H32B), C33(H33A,
 H33B), C34(H34A,H34B), C40(H40A,H40B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C26(H26),
 C27(H27), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46)
5.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C)
5.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O5(H5)
;
_shelx_res_checksum              64189
_shelx_hkl_checksum              68547
_shelx_fab_checksum              57372
_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 4.628
_oxdiff_exptl_absorpt_empirical_full_min 0.273