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_1562180
_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         'C67 H102 O4'
_chemical_formula_sum            'C67 H102 O4'
_chemical_formula_weight         971.48
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-06
_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
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.74070(10)
_cell_length_b                   27.9256(2)
_cell_length_c                   27.9774(2)
_cell_measurement_reflns_used    74253
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.9410
_cell_measurement_theta_min      4.0300
_cell_volume                     13860.55(16)
_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 0.995
_diffrn_measured_fraction_theta_max 0.990
_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  12.00   1.00    2.00    --    0.00  38.00-150.00   30
  2  \w    -30.00   7.00   1.00    2.00    --    0.00  77.00-120.00   37
  3  \w    -23.00  78.00   1.00    2.00    --    0.00  57.00  90.00  101
  4  \w     50.00  76.00   1.00    2.00    --    0.00  77.00-120.00   26
  5  \w    -19.00  84.00   1.00    2.00    --    0.00  38.00 -30.00  103
  6  \w     22.00  86.00   1.00    2.00    --    0.00  38.00-150.00   64
  7  \w    -17.00  86.00   1.00    2.00    --    0.00  38.00  30.00  103
  8  \w    -15.00  13.00   1.00    2.00    --    0.00  57.00-120.00   28
  9  \w    -18.00  20.00   1.00    2.00    --    0.00  38.00 150.00   38
 10  \w     -3.00  23.00   1.00    2.00    --    0.00 -57.00 -90.00   26
 11  \w    -89.00 -64.00   1.00    2.00    --    0.00 -57.00 -90.00   25
 12  \w     39.00  88.00   1.00    2.00    --    0.00  38.00 150.00   49
 13  \w    -27.00  70.00   1.00    2.00    --    0.00  82.00 150.00   97
 14  \w     46.00  84.00   1.00    2.00    --    0.00  57.00-120.00   38
 15  \w     19.00  45.00   1.00    2.00    --    0.00  77.00-120.00   26
 16  \w     64.00  90.00   1.00    5.00    --   95.80  79.00-130.44   26
 17  \w    154.00 182.00   1.00    5.00    --   95.80  79.00 110.44   28
 18  \w     68.00 184.00   1.00    5.00    --   95.80  69.00-145.88  116
 19  \w     64.00  89.00   1.00    5.00    --   95.80  79.00 110.44   25
 20  \w     66.00  91.00   1.00    5.00    --   95.80  75.00 171.06   25
 21  \w     71.00 168.00   1.00    5.00    --   95.80  60.00-151.59   97
 22  \w    145.00 172.00   1.00    5.00    --   95.80  47.00 111.64   27
 23  \w     96.00 124.00   1.00    5.00    --   95.80  76.00  19.54   28
 24  \w    127.00 163.00   1.00    5.00    --   95.80  76.00  19.54   36
 25  \w     65.00  90.00   1.00    5.00    --   95.80  77.00  79.18   25
 26  \w     67.00  92.00   1.00    5.00    --   95.80  71.00 157.29   25
 27  \w     65.00  91.00   1.00    5.00    --   95.80 -82.00  60.00   26
 28  \w     93.00 122.00   1.00    5.00    --   95.80 -82.00  60.00   29
 29  \w      6.00 125.00   1.00    5.00    --   95.80 -82.00-120.00  119
 30  \w     71.00 183.00   1.00    5.00    --   95.80  61.00 120.00  112
 31  \w     65.00  93.00   1.00    5.00    --   95.80  76.00  19.54   28
 32  \w     67.00  95.00   1.00    5.00    --   95.80  73.00  -4.26   28
 33  \w    149.00 175.00   1.00    5.00    --   95.80  72.00 -95.65   26
 34  \w     66.00  92.00   1.00    5.00    --   95.80  74.00 -36.99   26
 35  \w    107.00 171.00   1.00    5.00    --   95.80  78.00 -74.27   64
 36  \w     67.00  95.00   1.00    5.00    --   95.80  72.00 -95.65   28
 37  \w    146.00 183.00   1.00    5.00    --   95.80  71.00 -37.81   37
 38  \w     63.00  88.00   1.00    5.00    --   95.80  82.00-150.00   25
 39  \w     65.00 101.00   1.00    5.00    --   95.80  77.00  60.00   36
 40  \w     63.00  88.00   1.00    5.00    --   95.80  82.00-120.00   25
 41  \w     65.00  90.00   1.00    5.00    --   95.80  77.00 -90.00   25
 42  \w     63.00  89.00   1.00    5.00    --   95.80  82.00-180.00   26
 43  \w     63.00 128.00   1.00    5.00    --   95.80 -82.00 150.00   65
 44  \w     63.00  89.00   1.00    5.00    --   95.80  82.00   0.00   26
 45  \w     65.00  90.00   1.00    5.00    --   95.80  78.00 -74.27   25
 46  \w      7.00 126.00   1.00    5.00    --   95.80 -82.00  30.00  119
 47  \w     63.00  88.00   1.00    5.00    --   95.80  82.00 150.00   25
 48  \w     65.00  91.00   1.00    5.00    --   95.80  77.00 -60.00   26
 49  \w     65.00  91.00   1.00    5.00    --   95.80  77.00  90.00   26
 50  \w     65.00  90.00   1.00    5.00    --   95.80  77.00 120.00   25
 51  \w     63.00  89.00   1.00    5.00    --   95.80  82.00  30.00   26
 52  \w     65.00  90.00   1.00    5.00    --   95.80  77.00-180.00   25
 53  \w     95.00 121.00   1.00    5.00    --   95.80  77.00-180.00   26
 54  \w     65.00  94.00   1.00    5.00    --   95.80  77.00 -30.00   29
 55  \w     65.00 184.00   1.00    5.00    --   95.80  77.00  30.00  119
 56  \w     63.00  88.00   1.00    5.00    --   95.80  82.00 -90.00   25
 57  \w    114.00 140.00   1.00    5.00    --   95.80  82.00 -90.00   26
 58  \w     63.00  89.00   1.00    5.00    --   95.80  82.00  60.00   26
 59  \w     65.00  91.00   1.00    5.00    --   95.80  77.00-120.00   26
 60  \w     75.00 162.00   1.00    5.00    --   95.80  45.00 -90.00   87
 61  \w     66.00  91.00   1.00    5.00    --   95.80  74.00 136.01   25
 62  \w     65.00 137.00   1.00    5.00    --   95.80  77.00   0.00   72
 63  \w     71.00 140.00   1.00    5.00    --   95.80  61.00 -50.25   69
 64  \w     63.00  89.00   1.00    5.00    --   95.80  82.00 -30.00   26
 65  \w     99.00 125.00   1.00    5.00    --   95.80 -82.00-180.00   26
 66  \w    103.00 185.00   1.00    5.00    --   95.80  82.00  90.00   82
 67  \w     64.00 183.00   1.00    5.00    --   95.80  79.00  43.90  119
 68  \w      6.00  82.00   1.00    5.00    --   95.80 -82.00-180.00   76
 69  \w     63.00  88.00   1.00    5.00    --   95.80  82.00  90.00   25
 70  \w     48.00 125.00   1.00    5.00    --   95.80 -82.00   0.00   77
 71  \w     67.00 124.00   1.00    5.00    --   95.80 -82.00 -60.00   57
 72  \w    107.00 174.00   1.00    5.00    --   95.80  79.00-130.44   67
 73  \w     70.00 161.00   1.00    5.00    --   95.80  62.00 167.74   91
 74  \w     67.00  92.00   1.00    5.00    --   95.80  71.00 -37.81   25
 75  \w     75.00 111.00   1.00    5.00    --   95.80  47.00 111.64   36
 76  \w     72.00 182.00   1.00    5.00    --   95.80  56.00 -33.58  110
;
_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      0.0366676000
_diffrn_orient_matrix_UB_12      -0.0151649000
_diffrn_orient_matrix_UB_13      0.0475627000
_diffrn_orient_matrix_UB_21      0.0784743000
_diffrn_orient_matrix_UB_22      0.0031229000
_diffrn_orient_matrix_UB_23      -0.0233437000
_diffrn_orient_matrix_UB_31      0.0058886000
_diffrn_orient_matrix_UB_32      0.0529580000
_diffrn_orient_matrix_UB_33      0.0150153000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0933
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            384609
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.827
_diffrn_reflns_theta_min         3.538
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.422
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33554
_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    0.931
_exptl_crystal_description       block
_exptl_crystal_F_000             4288
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.203
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 10967 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1343
_refine_ls_number_reflns         28172
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0534P)^2^+2.1909P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1007
_refine_ls_wR_factor_ref         0.1029
_reflns_Friedel_coverage         0.858
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                26055
_reflns_number_total             28172
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00883h2.cif
_cod_data_source_block           exp_683
_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_cell_volume        13860.56(16)
_cod_original_formula_moiety     '2(C67 H102 O4)'
_cod_original_formula_sum        'C134 H204 O8'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     1942.96
_cod_database_code               1562180
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.823
_reflns_odcompleteness_completeness 99.93
_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, All O(H) groups
2. Rigid bond restraints
 C120, C123
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C120, C121
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C120, C122
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C33, C36
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C33, C34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C33, C35
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C116, C119
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C116, C118
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
C120 \\sim C123: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C108 \\sim C110: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C108 \\sim C111: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C109 \\sim C108: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C120 \\sim C121: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C123 \\sim C120: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C122 \\sim C120: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C33 \\sim C36: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C33 \\sim C35: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C33 \\sim C34: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C37 \\sim C38: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C40 \\sim C37: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C37 \\sim C39: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
4.a Ternary CH refined with riding coordinates:
 C125(H125), C126(H126), C127(H127), C130(H130), C58(H58), C59(H59), C60(H60),
 C63(H63)
4.b Aromatic/amide H refined with riding coordinates:
 C69(H69), C71(H71), C73(H73), C75(H75), C77(H77), C79(H79), C81(H81),
 C83(H83), C85(H85), C87(H87), C89(H89), C91(H91), C2(H2), C4(H4A), C6(H6),
 C8(H8), C10(H10), C12(H12), C14(H14), C16(H16), C18(H18), C20(H20), C22(H22),
 C24(H24)
4.c Tetrahedral OH refined with riding coordinates:
 O5(H5), O3(H3)
4.d Idealised Me refined as rotating group:
 C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C101(H10A,H10B,H10C),
 C102(H10D,H10E,H10F), C103(H10G,H10H,H10I), C105(H10J,H10K,H10L), C106(H10M,
 H10N,H10O), C107(H10P,H10Q,H10R), C109(H10S,H10T,H10U), C110(H11A,H11B,H11C),
 C111(H11D,H11E,H11F), C113(H11G,H11H,H11I), C114(H11J,H11K,H11L), C115(H11M,
 H11N,H11O), C117(H11P,H11Q,H11R), C118(H11S,H11T,H11U), C119(H11V,H11W,H11X),
 C121(H12A,H12B,H12C), C122(H12D,H12E,H12F), C123(H12G,H12H,H12I), C128(H12J,
 H12K,H12L), C129(H12M,H12N,H12O), C131(H13A,H13B,H13C), C132(H13D,H13E,H13F),
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C50(H50A,
 H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C),
 C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C61(H61A,H61B,H61C), C62(H62A,H62B,
 H62C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C)
;
_shelx_res_checksum              47128
_shelx_hkl_checksum              52593
_shelx_fab_checksum              69808
_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 2.547
_oxdiff_exptl_absorpt_empirical_full_min 0.427