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_1562179
_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         'C39 H21 F24 O4, C39 H22 F24 O4'
_chemical_formula_sum            'C78 H43 F48 O8'
_chemical_formula_weight         2020.12
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-13
_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                 111.3170(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.53300(10)
_cell_length_b                   32.5011(2)
_cell_length_c                   12.42090(10)
_cell_measurement_reflns_used    57042
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      74.3100
_cell_measurement_theta_min      4.0630
_cell_volume                     3961.18(6)
_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(11)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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    -18.00  78.00   1.00    1.00    --    0.00  38.00  30.00   96
  2  \w     26.00  63.00   1.00    1.00    --    0.00  57.00 120.00   37
  3  \w     54.00  84.00   1.00    1.00    --    0.00  57.00-150.00   30
  4  \w    -19.00  88.00   1.00    1.00    --    0.00  38.00  90.00  107
  5  \w    -22.00  18.00   1.00    1.00    --    0.00  57.00 120.00   40
  6  \w    -17.00  88.00   1.00    1.00    --    0.00  38.00 -30.00  105
  7  \w    -16.00  89.00   1.00    1.00    --    0.00  38.00 -90.00  105
  8  \w    -20.00  53.00   1.00    1.00    --    0.00  57.00-150.00   73
  9  \w    -32.00  67.00   1.00    1.00    --    0.00  82.00 150.00   99
 10  \w     66.00  92.00   1.00    1.00    --   95.80  74.00  54.92   26
 11  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-104.90   26
 12  \w    152.00 178.00   1.00    1.00    --   95.80  74.00 141.30   26
 13  \w    138.00 182.00   1.00    1.00    --   95.80  82.00-104.90   44
 14  \w     63.00  90.00   1.00    1.00    --   95.80  82.00 102.58   27
 15  \w    150.00 178.00   1.00    1.00    --   95.80  60.00 -46.30   28
 16  \w     73.00 134.00   1.00    1.00    --   95.80  54.00  -5.25   61
 17  \w     66.00  92.00   1.00    1.00    --   95.80  74.00 141.30   26
 18  \w    129.00 156.00   1.00    1.00    --   95.80  77.00  30.00   27
 19  \w      6.00 127.00   1.00    1.00    --   95.80 -82.00   0.00  121
 20  \w    102.00 129.00   1.00    1.00    --   95.80  79.00 164.40   27
 21  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 22  \w     46.00 127.00   1.00    1.00    --   95.80 -82.00  90.00   81
 23  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  60.00   26
 24  \w     63.00  90.00   1.00    1.00    --   95.80  82.00  90.00   27
 25  \w     63.00  90.00   1.00    1.00    --   95.80  82.00 -60.00   27
 26  \w     63.00  90.00   1.00    1.00    --   95.80  82.00 -90.00   27
 27  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 28  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-150.00   26
 29  \w      6.00 126.00   1.00    1.00    --   95.80 -77.00  30.00  120
 30  \w     71.00 181.00   1.00    1.00    --   95.80  61.00   0.00  110
 31  \w     71.00 134.00   1.00    1.00    --   95.80  60.00 -46.30   63
 32  \w      7.00 123.00   1.00    1.00    --   95.80 -82.00-180.00  116
 33  \w     75.00 185.00   1.00    1.00    --   95.80  45.00-120.00  110
 34  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -60.00   26
 35  \w    133.00 167.00   1.00    1.00    --   95.80  82.00-144.66   34
 36  \w     65.00  90.00   1.00    1.00    --   95.80  79.00 164.40   25
 37  \w     64.00  89.00   1.00    1.00    --   95.80  82.00-120.00   25
 38  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  60.00   26
 39  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -30.00   26
 40  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 41  \w     72.00  99.00   1.00    1.00    --   95.80  61.00 120.00   27
 42  \w     71.00  97.00   1.00    1.00    --   95.80  61.00 -60.00   26
 43  \w     71.00 162.00   1.00    1.00    --   95.80  61.00 -30.00   91
 44  \w     72.00  99.00   1.00    1.00    --   95.80  61.00  90.00   27
 45  \w    129.00 171.00   1.00    1.00    --   95.80  61.00  90.00   42
 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  82.00-180.00   26
 48  \w     47.00 122.00   1.00    1.00    --   95.80 -82.00 -90.00   75
 49  \w     75.00 146.00   1.00    1.00    --   95.80  45.00 120.00   71
 50  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-144.66   26
 51  \w     71.00  97.00   1.00    1.00    --   95.80  61.00 -90.00   26
 52  \w     72.00 185.00   1.00    1.00    --   95.80  61.00  30.00  113
 53  \w     72.00 125.00   1.00    1.00    --   95.80  61.00 150.00   53
 54  \w    129.00 160.00   1.00    1.00    --   95.80  61.00 150.00   31
 55  \w     65.00  91.00   1.00    1.00    --   95.80  77.00   0.00   26
 56  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 120.00   26
 57  \w     76.00 173.00   1.00    1.00    --   95.80  45.00-150.00   97
 58  \w     75.00 181.00   1.00    1.00    --   95.80  45.00 -90.00  106
 59  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 150.00   26
 60  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -30.00   26
 61  \w     65.00  95.00   1.00    1.00    --   95.80  77.00-180.00   30
 62  \w     99.00 180.00   1.00    1.00    --   95.80  82.00 102.58   81
 63  \w     68.00 184.00   1.00    1.00    --   95.80  68.00  53.08  116
 64  \w     66.00  92.00   1.00    1.00    --   95.80  74.00  29.18   26
 65  \w     71.00  99.00   1.00    1.00    --   95.80  61.00-180.00   28
 66  \w     20.00 126.00   1.00    1.00    --   95.80 -77.00-150.00  106
 67  \w    131.00 156.00   1.00    1.00    --   95.80  57.00  19.68   25
 68  \w     72.00  98.00   1.00    1.00    --   95.80  57.00  19.68   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      -0.0420230000
_diffrn_orient_matrix_UB_12      0.0285868000
_diffrn_orient_matrix_UB_13      -0.1062081000
_diffrn_orient_matrix_UB_21      -0.0801074000
_diffrn_orient_matrix_UB_22      -0.0355747000
_diffrn_orient_matrix_UB_23      -0.0767767000
_diffrn_orient_matrix_UB_31      -0.1283087000
_diffrn_orient_matrix_UB_32      0.0128671000
_diffrn_orient_matrix_UB_33      0.0234274000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0472
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            103203
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.783
_diffrn_reflns_theta_min         4.055
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.685
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.21928
_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    1.694
_exptl_crystal_description       block
_exptl_crystal_F_000             2014
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.719
_refine_diff_density_min         -0.465
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 7220 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   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1250
_refine_ls_number_reflns         15951
_refine_ls_number_restraints     100
_refine_ls_restrained_S_all      1.177
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0454
_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^)+(0.0528P)^2^+4.5068P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1127
_refine_ls_wR_factor_ref         0.1131
_reflns_Friedel_coverage         0.947
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.972
_reflns_number_gt                15675
_reflns_number_total             15951
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00883h2.cif
_cod_data_source_block           exp_809
_cod_depositor_comments
'Adding full bibliography for 1562171--1562180.cif.'
_cod_database_code               1562179
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.751
_shelx_estimated_absorpt_t_min   0.498
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C28-F7 = C28-F8 = C28-F9
 1.32 with sigma of 0.01
 C28-F7' = C28-F8' = C28-F9'
 1.32 with sigma of 0.01
 C28-F7 \\sim C28-F8 \\sim C28-F9 \\sim C28-F7' \\sim C28-F8' \\sim C28-F9'
 with sigma of 0.02
 F7-F7' \\sim F7'-F8 \\sim F8-F8' \\sim F8'-F9 \\sim F9-F9' \\sim F9'-F7
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F7 \\sim F8 \\sim F9 \\sim F7' \\sim F8' \\sim F9': within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(F25) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7') \\sim Ueq, Uanis(F26)
\\sim Ueq, Uanis(F8') \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.004
Uanis(F2) \\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(F25) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(F26) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Others
 Fixed Sof: F7(0.5) F8(0.5) F9(0.5) F7'(0.5) F8'(0.5) F9'(0.5)
5.a Ternary CH refined with riding coordinates:
 C74(H74), C75(H75), C35(H35), C36(H36)
5.b Aromatic/amide H refined with riding coordinates:
 C41(H41), C43(H43), C45(H45), C47(H47), C49(H49), C51(H51), C53(H53),
 C55(H55), C57(H57), C59(H59), C61(H61), C63(H63), C2(H2A), C4(H4), C6(H6),
 C8(H8), C10(H10), C12(H12), C14(H14), C16(H16), C18(H18), C20(H20), C22(H22),
 C24(H24)
5.c Idealised Me refined as rotating group:
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C)
;
_shelx_res_checksum              70035
_shelx_hkl_checksum              80179
_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 4.184
_oxdiff_exptl_absorpt_empirical_full_min 0.636