A Giese reaction for electron-rich alkenes.
Huang, Qi; Suravarapu, Sankar Rao; Renaud, Philippe; Chemical science 12 (2020) 2225–2230; doi:10.1039/d0sc06341j

data_1559816
_publ_section_title
;
 A Giese reaction for electron-rich alkenes.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              2225
_journal_page_last               2230
_journal_paper_doi               10.1039/d0sc06341j
_journal_volume                  12
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H36 O4'
_chemical_formula_sum            'C25 H36 O4'
_chemical_formula_weight         400.54
_chemical_name_systematic
'(3S,8S,9S,10R,13S,14S,17S)-10,13-Dimethyl-17-((R)-5-oxotetrahydrofuran-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate'
_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
_audit_creation_date             2020-07-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-09-10 deposited with the CCDC.	2020-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.5319(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.15180(6)
_cell_length_b                   60.5855(6)
_cell_length_c                   6.15597(7)
_cell_measurement_reflns_used    28664
_cell_measurement_temperature    90.0(9)
_cell_measurement_theta_max      74.0230
_cell_measurement_theta_min      2.2400
_cell_volume                     2199.54(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.72a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.72a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.72a (Rigaku OD, 2020)'
_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      90.0(9)
_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 0.994
_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    -77.00  -3.66   0.38    0.10    --  -24.75 112.00 -95.00  193
  2  \w     25.00  91.88   0.38    0.10    --   39.91-112.00 171.00  176
  3  \w     30.00 108.28   0.38    0.10    --  109.15-112.00 171.00  206
  4  \w    103.00 169.88   0.38    0.10    --  109.15 112.00 -95.00  176
  5  \w   -100.00   2.22   0.38    0.10    --  -24.75 -57.00   0.00  269
  6  \w   -100.00   2.22   0.38    0.10    --  -24.75 -57.00  90.00  269
  7  \w   -104.00   4.30   0.38    0.10    --  -24.75 -45.00  90.00  285
  8  \w   -100.00   2.22   0.38    0.10    --  -24.75 -57.00-180.00  269
  9  \w    -44.00  21.74   0.38    0.10    --   39.91 -19.00  90.00  173
 10  \w    -44.00  21.74   0.38    0.10    --   39.91 -19.00 150.00  173
 11  \w     -1.00  84.88   0.38    0.10    --   39.91 -99.00   0.00  226
 12  \w    -44.00  21.74   0.38    0.10    --   39.91 -19.00  30.00  173
 13  \w    -35.00  61.14   0.38    0.10    --   39.91 -57.00-150.00  253
 14  \w    -44.00  21.74   0.38    0.10    --   39.91 -19.00 -30.00  173
 15  \w     29.00 105.00   0.38    0.10    --  109.15 -94.00  60.00  200
 16  \w     80.00 170.06   0.38    0.10    --  109.15  45.00 -30.00  237
 17  \w     80.00 170.06   0.38    0.10    --  109.15  61.00 150.00  237
 18  \w     35.00 111.00   0.38    0.10    --  109.15-125.00   0.00  200
 19  \w     75.00 170.00   0.38    0.10    --  109.15  77.00  60.00  250
 20  \w     29.00 105.00   0.38    0.10    --  109.15 -94.00-180.00  200
 21  \w     35.00 111.00   0.38    0.10    --  109.15-125.00 -30.00  200
 22  \w     80.00 170.06   0.38    0.10    --  109.15  61.00-180.00  237
 23  \w     34.00  67.06   0.38    0.10    --  109.15 -61.00-180.00   87
 24  \w     28.00 105.14   0.38    0.10    --  109.15 -99.00-173.22  203
 25  \w     75.00 170.00   0.38    0.10    --  109.15  77.00-120.00  250
 26  \w     95.00 171.00   0.38    0.10    --  109.15 125.00-120.00  200
 27  \w     34.00  67.06   0.38    0.10    --  109.15 -61.00 150.00   87
 28  \w     29.00 105.00   0.38    0.10    --  109.15 -94.00 -30.00  200
 29  \w     80.00 170.06   0.38    0.10    --  109.15  45.00  60.00  237
 30  \w     95.00 171.00   0.38    0.10    --  109.15 125.00   0.00  200
 31  \w     34.00  67.06   0.38    0.10    --  109.15 -61.00-150.00   87
 32  \w     80.00 170.06   0.38    0.10    --  109.15  61.00   0.00  237
 33  \w     34.00 100.88   0.38    0.10    --  109.15 -77.00  60.00  176
 34  \w     34.00  67.06   0.38    0.10    --  109.15 -61.00   0.00   87
 35  \w     34.00  67.06   0.38    0.10    --  109.15 -61.00 -60.00   87
 36  \w   -109.00 -42.12   0.38    0.10    --  -24.75-177.00  60.00  176
 37  \w      6.00 115.06   0.38    0.10    --   39.91  77.00 -60.00  287
 38  \w      6.00 115.06   0.38    0.10    --   39.91  77.00  30.00  287
 39  \w      9.00 120.34   0.38    0.10    --   39.91  38.00 150.00  293
 40  \w      6.00 115.06   0.38    0.10    --   39.91  77.00-150.00  287
 41  \w      6.00 115.06   0.38    0.10    --   39.91  77.00  60.00  287
 42  \w      6.00 115.06   0.38    0.10    --   39.91  77.00 120.00  287
 43  \w     13.00 115.22   0.38    0.10    --   39.91  57.00-150.00  269
 44  \w      6.00 115.06   0.38    0.10    --   39.91  77.00 -90.00  287
 45  \w     13.00 115.22   0.38    0.10    --   39.91  57.00-120.00  269
 46  \w      6.00 115.06   0.38    0.10    --   39.91  77.00 150.00  287
 47  \w      9.00 120.34   0.38    0.10    --   39.91  38.00 -30.00  293
 48  \w     72.00 170.04   0.38    0.10    --  109.15  30.00 150.00  258
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1384148000
_diffrn_orient_matrix_UB_12      0.0196088000
_diffrn_orient_matrix_UB_13      -0.0489761000
_diffrn_orient_matrix_UB_21      -0.2037328000
_diffrn_orient_matrix_UB_22      0.0154187000
_diffrn_orient_matrix_UB_23      -0.0192942000
_diffrn_orient_matrix_UB_31      0.0871054000
_diffrn_orient_matrix_UB_32      0.0049061000
_diffrn_orient_matrix_UB_33      0.2557319000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       75
_diffrn_reflns_limit_k_min       -74
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            41608
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.306
_diffrn_reflns_theta_min         2.188
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.634
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48776
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.72a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.210
_exptl_crystal_description       plate
_exptl_crystal_F_000             872
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: heptane/diethylether'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.263
_refine_diff_density_min         -0.305
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 3906 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     530
_refine_ls_number_reflns         8784
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0486
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0586P)^2^+1.1783P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1155
_refine_ls_wR_factor_ref         0.1192
_reflns_Friedel_coverage         0.972
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                8466
_reflns_number_total             8784
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc06341j2.cif
_cod_data_source_block           20PR011_QH598-P1
_cod_depositor_comments
;Adding full bibliography for 1559814--1559816.cif.

 Adding full bibliography for 1559814--1559816.cif.
;
_cod_original_cell_volume        2199.55(4)
_cod_database_code               1559816
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H30O4
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.868
_diffrn_oxdiff_digest_frames
;
01e3e39f0eb9b1161519a2901f702ae24a001030e50
;
_diffrn_oxdiff_digest_hkl
;
014ba689a6f8915f0101ffc9ed861ec17ab6f2
;
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8014(19)
 0.1986(19)
2. 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
3.a Ternary CH refined with riding coordinates:
 C14(H14), C45(H45), C41(H41), C42(H42), C19(H19), C15(H15), C34(H34),
 C53(H53), C21(H21), C51(H51), C5(H5), C24(H24)
3.b Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C39(H39A,H39B), C9(H9A,H9B), C16(H16A,H16B), C13(H13A,H13B),
 C17(H17A,H17B), C47(H47A,H47B), C23(H23A,H23B), C50(H50A,H50B), C43(H43A,H43B),
  C35(H35A,H35B), C48(H48A,H48B), C6(H6A,H6B), C22(H22A,H22B), C10(H10A,H10B),
 C54(H54A,H54B), C36(H36A,H36B), C25(H25A,H25B), C26(H26A,H26B), C55(H55A,H55B)
3.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C44(H44)
3.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C11(H11A,H11B,H11C), C52(H52A,H52B,H52C), C20(H20A,H20B,
 H20C), C1(H1A,H1B,H1C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              71675
_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 1.725
_oxdiff_exptl_absorpt_empirical_full_min 0.588