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_1562174
_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         'C19 H24 O4'
_chemical_formula_sum            'C19 H24 O4'
_chemical_formula_weight         316.38
_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             2019-03-04
_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                 90.9350(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.10660(10)
_cell_length_b                   17.4846(2)
_cell_length_c                   11.70950(10)
_cell_measurement_reflns_used    24822
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.1260
_cell_measurement_theta_min      3.7760
_cell_volume                     1659.49(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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.980
_diffrn_measured_fraction_theta_max 0.975
_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     32.00  76.00   1.00    1.00    --    0.00  56.00  34.00   44
  2  \w     -5.00  21.00   1.00    1.00    --    0.00  56.00  34.00   26
  3  \w     70.00 117.00   1.00    1.00    --   95.80 -56.00-107.00   47
  4  \w     72.00 153.00   1.00    1.00    --   95.80  56.00  34.00   81
  5  \w    -23.00  10.00   1.00    1.00    --    0.00  57.00  60.00   33
  6  \w    -23.00   2.00   1.00    1.00    --    0.00 -77.00   0.00   25
  7  \w    -22.00  18.00   1.00    1.00    --    0.00 -38.00 120.00   40
  8  \w    -23.00  34.00   1.00    1.00    --    0.00  19.00  30.00   57
  9  \w    -69.00 -42.00   1.00    1.00    --    0.00 -38.00 120.00   27
 10  \w    -41.00  22.00   1.00    1.00    --    0.00 -56.00-107.00   63
 11  \w    -80.00 -37.00   1.00    1.00    --    0.00 -77.00   0.00   43
 12  \w    -23.00  43.00   1.00    1.00    --    0.00  57.00 120.00   66
 13  \w    -23.00  78.00   1.00    1.00    --    0.00  57.00 -90.00  101
 14  \w     52.00  79.00   1.00    1.00    --    0.00  19.00  30.00   27
 15  \w     15.00  85.00   1.00    1.00    --    0.00  57.00  60.00   70
 16  \w    -18.00  89.00   1.00    1.00    --    0.00  38.00-150.00  107
 17  \w     64.00  89.00   1.00    1.00    --   95.80  82.00 120.00   25
 18  \w    125.00 184.00   1.00    1.00    --   95.80  82.00  30.00   59
 19  \w    131.00 180.00   1.00    1.00    --   95.80  82.00 -30.00   49
 20  \w     63.00  90.00   1.00    1.00    --   95.80  82.00  30.00   27
 21  \w     72.00 184.00   1.00    1.00    --   95.80  61.00-150.00  112
 22  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 23  \w    117.00 185.00   1.00    1.00    --   95.80  61.00 -90.00   68
 24  \w     10.00  35.00   1.00    1.00    --   95.80 -82.00-120.00   25
 25  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 150.00   25
 26  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 150.00   26
 27  \w     42.00 125.00   1.00    1.00    --   95.80 -82.00-120.00   83
 28  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  97.47   26
 29  \w     71.00  98.00   1.00    1.00    --   95.80  70.00 -37.13   27
 30  \w    113.00 172.00   1.00    1.00    --   95.80  70.00 -37.13   59
 31  \w     65.00  97.00   1.00    1.00    --   95.80  77.00-150.00   32
 32  \w     72.00  97.00   1.00    1.00    --   95.80  59.00  12.73   25
 33  \w    151.00 176.00   1.00    1.00    --   95.80  59.00  12.73   25
 34  \w     69.00 129.00   1.00    1.00    --   95.80  65.00 -52.63   60
 35  \w    157.00 183.00   1.00    1.00    --   95.80  80.00  74.59   26
 36  \w     64.00  90.00   1.00    1.00    --   95.80  80.00  74.59   26
 37  \w     10.00 117.00   1.00    1.00    --   95.80 -82.00-180.00  107
 38  \w    139.00 184.00   1.00    1.00    --   95.80  77.00 169.95   45
 39  \w     69.00 159.00   1.00    1.00    --   95.80  65.00  41.84   90
 40  \w    125.00 178.00   1.00    1.00    --   95.80  62.00 109.49   53
 41  \w    104.00 162.00   1.00    1.00    --   95.80  61.00 -60.00   58
 42  \w     70.00 118.00   1.00    1.00    --   95.80  62.00 109.49   48
 43  \w     65.00  92.00   1.00    1.00    --   95.80  77.00 120.00   27
 44  \w     65.00  92.00   1.00    1.00    --   95.80  77.00   0.00   27
 45  \w     65.00  94.00   1.00    1.00    --   95.80  77.00-120.00   29
 46  \w     66.00  91.00   1.00    1.00    --   95.80  77.00 -60.00   25
 47  \w     73.00 103.00   1.00    1.00    --   95.80  61.00 -60.00   30
 48  \w     75.00 137.00   1.00    1.00    --   95.80  45.00-180.00   62
 49  \w     75.00 148.00   1.00    1.00    --   95.80  45.00   0.00   73
 50  \w     63.00  90.00   1.00    1.00    --   95.80  82.00-180.00   27
 51  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 52  \w     50.00 128.00   1.00    1.00    --   95.80 -82.00  90.00   78
 53  \w    121.00 182.00   1.00    1.00    --   95.80  45.00  90.00   61
 54  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  60.00   26
 55  \w    122.00 148.00   1.00    1.00    --   95.80  77.00 -90.00   26
 56  \w     72.00 121.00   1.00    1.00    --   95.80  61.00  90.00   49
 57  \w     66.00  93.00   1.00    1.00    --   95.80  82.00   0.00   27
 58  \w     77.00 106.00   1.00    1.00    --   95.80  30.00-180.00   29
 59  \w     76.00 101.00   1.00    1.00    --   95.80  45.00 -60.00   25
 60  \w     73.00 100.00   1.00    1.00    --   95.80  61.00   0.00   27
 61  \w     92.00 127.00   1.00    1.00    --   95.80 -82.00 -60.00   35
 62  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 63  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 64  \w     65.00  92.00   1.00    1.00    --   95.80  77.00  90.00   27
 65  \w     65.00 185.00   1.00    1.00    --   95.80  77.00-129.38  120
 66  \w     69.00 184.00   1.00    1.00    --   95.80  66.00 123.36  115
 67  \w    148.00 173.00   1.00    1.00    --   95.80  82.00 120.00   25
 68  \w     76.00 102.00   1.00    1.00    --   95.80  45.00  90.00   26
 69  \w     66.00 116.00   1.00    1.00    --   95.80  77.00 169.95   50
 70  \w      7.00 125.00   1.00    1.00    --   95.80 -82.00  30.00  118
 71  \w     71.00  98.00   1.00    1.00    --   95.80  61.00 -90.00   27
;
_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      0.0313657000
_diffrn_orient_matrix_UB_12      -0.0480240000
_diffrn_orient_matrix_UB_13      -0.1076455000
_diffrn_orient_matrix_UB_21      -0.1530653000
_diffrn_orient_matrix_UB_22      0.0358162000
_diffrn_orient_matrix_UB_23      -0.0584194000
_diffrn_orient_matrix_UB_31      0.1083419000
_diffrn_orient_matrix_UB_32      0.0646258000
_diffrn_orient_matrix_UB_33      -0.0479086000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0539
_diffrn_reflns_av_unetI/netI     0.0283
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            39997
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.560
_diffrn_reflns_theta_min         4.545
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.709
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40544
_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    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.32
_refine_diff_density_max         0.929
_refine_diff_density_min         -0.503
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 2907 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         6567
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0800P)^2^+0.2564P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1165
_refine_ls_wR_factor_ref         0.1174
_reflns_Friedel_coverage         0.920
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.960
_reflns_number_gt                6366
_reflns_number_total             6567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00883h2.cif
_cod_data_source_block           exp_677
_cod_depositor_comments
;
Adding full bibliography for 1562171--1562180.cif.

2022-05-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C19 H24 O4)'
_cod_original_formula_sum        'C38 H48 O8'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     632.76
_cod_database_code               1562174
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.805
_shelx_estimated_absorpt_t_min   0.736
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C19-C18
 1.32 with sigma of 0.01
3. Rigid bond restraints
 C19, C18
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C18, C19
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C19 \\sim C18: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.08
C18 \\sim C19: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
5.a Ternary CH refined with riding coordinates:
 C7(H7), C13(H13), C25(H25), C31(H31)
5.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C17(H17A,H17B),
 C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C32(H32A,H32B), C38(H38A,H38B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3A), C18(H18), C21(H21), C22(H22), C37(H37)
5.d X=CH2 refined with riding coordinates:
 C19(H19A,H19B), C36(H36A,H36B)
5.e Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C)
5.f Idealised tetrahedral OH refined as rotating group:
 O3(H3), O7(H7A)
;
_shelx_res_checksum              21716
_shelx_hkl_checksum              5145
_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 2.122
_oxdiff_exptl_absorpt_empirical_full_min 0.566