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_1559815
_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         'C29 H46 O4 Si'
_chemical_formula_sum            'C29 H46 O4 Si'
_chemical_formula_weight         486.75
_chemical_name_systematic
'Ethyl 2-((8R,9S,13S,14S,16S,17S)-17-((tert-butyldimethylsilyl)oxy)-3-methoxy- 13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-16-yl)acetate'
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-08-07
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2020-09-10 deposited with the CCDC.	2020-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                101.7853(5)
_cell_angle_beta                 91.4615(5)
_cell_angle_gamma                98.5773(5)
_cell_formula_units_Z            2
_cell_length_a                   6.44725(4)
_cell_length_b                   10.18619(6)
_cell_length_c                   22.76512(12)
_cell_measurement_reflns_used    24477
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      78.7530
_cell_measurement_theta_min      3.9610
_cell_volume                     1444.746(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_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      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -56.00   8.00   0.50    1.00    --  -21.00 103.00 -66.00  128
  2  \w     42.00 107.00   0.50    5.00    --  113.25-103.00-168.00  130
  3  \w    106.00 171.00   0.50    5.00    --  113.25 103.00 -66.00  130
  4  \w    -68.00 -12.00   0.50    1.00    --  -21.00 125.00 -30.00  112
  5  \w    -68.00 -12.00   0.50    1.00    --  -21.00 125.00 -90.00  112
  6  \w    -93.00  -5.00   0.50    1.00    --  -21.00 -57.00-180.00  176
  7  \w    -26.00  23.00   0.50    1.00    --   47.89 -19.00 -90.00   98
  8  \w     33.00 121.00   0.50    1.00    --   47.89  57.00  30.00  176
  9  \w    -26.00  23.00   0.50    1.00    --   47.89 -19.00-180.00   98
 10  \w    -26.00  23.00   0.50    1.00    --   47.89 -19.00-120.00   98
 11  \w    -26.00  23.00   0.50    1.00    --   47.89 -19.00  60.00   98
 12  \w     15.00  84.00   0.50    1.00    --   47.89-103.00-168.00  138
 13  \w    101.00 171.00   0.50    5.00    --  113.25  30.00 120.00  140
 14  \w     42.00 102.00   0.50    5.00    --  113.25 -77.00 120.00  120
 15  \w     42.00  68.00   0.50    5.00    --  113.25 -61.00-150.00   52
 16  \w     42.00 106.00   0.50    5.00    --  113.25 -94.00 -30.00  128
 17  \w     91.00 171.00   0.50    5.00    --  113.25  77.00 -30.00  160
 18  \w     91.00 171.00   0.50    5.00    --  113.25  77.00-150.00  160
 19  \w     42.00 106.00   0.50    5.00    --  113.25 -94.00-180.00  128
 20  \w     42.00  68.00   0.50    5.00    --  113.25 -61.00 120.00   52
 21  \w     42.00  68.00   0.50    5.00    --  113.25 -61.00   0.00   52
 22  \w     42.00 106.00   0.50    5.00    --  113.25 -94.00  90.00  128
 23  \w     42.00  68.00   0.50    5.00    --  113.25 -61.00 -30.00   52
 24  \w     42.00 112.00   0.50    5.00    --  113.25-125.00  90.00  140
 25  \w    100.00 171.00   0.50    5.00    --  113.25  15.00-120.00  142
 26  \w     42.00 106.00   0.50    5.00    --  113.25 -94.00-150.00  128
 27  \w     97.00 171.00   0.50    5.00    --  113.25  61.00 150.00  148
 28  \w    100.00 171.00   0.50    5.00    --  113.25  15.00 -60.00  142
 29  \w     42.00 106.00   0.50    5.00    --  113.25 -94.00 -90.00  128
 30  \w    101.00 171.00   0.50    5.00    --  113.25  30.00 -90.00  140
 31  \w    101.00 171.00   0.50    5.00    --  113.25  45.00  30.00  140
 32  \w     42.00 112.00   0.50    5.00    --  113.25-125.00-180.00  140
 33  \w     42.00  68.00   0.50    5.00    --  113.25 -61.00  90.00   52
 34  \w     42.00 112.00   0.50    5.00    --  113.25-125.00  60.00  140
 35  \w     95.00 171.00   0.50    5.00    --  113.25 125.00 -30.00  152
 36  \w    101.00 171.00   0.50    5.00    --  113.25  30.00   0.00  140
 37  \w     42.00 112.00   0.50    5.00    --  113.25-125.00 120.00  140
 38  \w     97.00 171.00   0.50    5.00    --  113.25  61.00  90.00  148
 39  \w     42.00 106.00   0.50    5.00    --  113.25 -94.00 -60.00  128
 40  \w     42.00  68.00   0.50    5.00    --  113.25 -61.00-120.00   52
 41  \w     42.00 102.00   0.50    5.00    --  113.25 -77.00 -30.00  120
 42  \w     42.00  68.00   0.50    5.00    --  113.25 -61.00 -90.00   52
 43  \w    -68.00 -12.00   0.50    1.00    --  -21.00 125.00 150.00  112
 44  \w     26.00 121.00   0.50    1.00    --   47.89  77.00  90.00  190
 45  \w     33.00 121.00   0.50    1.00    --   47.89  57.00 -90.00  176
 46  \w     26.00 121.00   0.50    1.00    --   47.89  77.00-180.00  190
 47  \w     26.00 121.00   0.50    1.00    --   47.89  77.00  30.00  190
 48  \w     26.00 121.00   0.50    1.00    --   47.89  77.00 120.00  190
 49  \w     26.00 110.00   0.50    1.00    --   47.89  77.00-120.00  168
 50  \w     26.00 121.00   0.50    1.00    --   47.89  77.00 -60.00  190
;
_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      -0.1729792000
_diffrn_orient_matrix_UB_12      0.0563513000
_diffrn_orient_matrix_UB_13      -0.0306044000
_diffrn_orient_matrix_UB_21      0.1145732000
_diffrn_orient_matrix_UB_22      -0.0200911000
_diffrn_orient_matrix_UB_23      -0.0589725000
_diffrn_orient_matrix_UB_31      -0.1246691000
_diffrn_orient_matrix_UB_32      -0.1445656000
_diffrn_orient_matrix_UB_33      -0.0195065000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0301
_diffrn_reflns_av_unetI/netI     0.0277
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            29329
_diffrn_reflns_point_group_measured_fraction_full 0.858
_diffrn_reflns_point_group_measured_fraction_max 0.840
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.501
_diffrn_reflns_theta_min         3.974
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.945
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.590
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.119
_exptl_crystal_description       needle
_exptl_crystal_F_000             532
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Diethylether'
_exptl_crystal_size_max          0.251
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.045
_refine_diff_density_max         0.565
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 3694 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     629
_refine_ls_number_reflns         9878
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0501
_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^)+(0.1029P)^2^+0.3937P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1380
_refine_ls_wR_factor_ref         0.1512
_reflns_Friedel_coverage         0.683
_reflns_Friedel_fraction_full    0.717
_reflns_Friedel_fraction_max     0.682
_reflns_number_gt                9500
_reflns_number_total             9878
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc06341j2.cif
_cod_data_source_block           20pr012_absorption
_cod_depositor_comments
;Adding full bibliography for 1559814--1559816.cif.

 Adding full bibliography for 1559814--1559816.cif.
;
_cod_database_code               1559815
_shelx_shelxl_version_number     2016/4
_chemical_oxdiff_formula         C29H46O4Si
_diffrn_oxdiff_digest_frames
;
013244d805f3bce19929e5bf7ae48919fa0644402f9
;
_diffrn_oxdiff_digest_hkl
;
01242369a0dbfcfe40deb7ff6df98c50373c03
;
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
2.a Ternary CH refined with riding coordinates:
 C17B(H17C), C10B(H10C), C11B(H11C), C9B(H9B), C8A(H8A), C15A(H15A),
 C16B(H16B), C7A(H7A), C16A(H16A), C14A(H14A)
2.b Secondary CH2 refined with riding coordinates:
 C15B(H15B,H15C), C11A(H11A,H11B), C12A(H12A,H12B), C14B(H14B,H14C), C8B(H8BA,
 H8BB), C13B(H13A,H13B), C7B(H7BA,H7BB), C9A(H9AA,H9AB), C20B(H20C,H20D),
 C10A(H10A,H10B), C17A(H17A,H17B), C22B(H22C,H22D), C20A(H20A,H20B), C22A(H22A,
 H22B)
2.c Aromatic/amide H refined with riding coordinates:
 C6A(H6A), C2B(H2B), C6B(H6B), C5B(H5B), C2A(H2A), C3A(H3A)
2.d Idealised Me refined as rotating group:
 C18B(H18D,H18E,H18F), C19B(H19D,H19E,H19F), C18A(H18A,H18B,H18C), C19A(H19A,
 H19B,H19C), C24B(H24D,H24E,H24F), C27A(H27A,H27B,H27C), C28A(H28A,H28B,H28C),
 C24A(H24A,H24B,H24C), C29A(H29A,H29B,H29C), C28B(H28D,H28E,H28F), C25A(H25A,
 H25B,H25C), C25B(H25D,H25E,H25F), C29B(H29D,H29E,H29F), C27B(H27D,H27E,H27F),
 C23B(H23D,H23E,H23F), C23A(H23A,H23B,H23C)
;
_shelx_res_checksum              78235
_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 2.245
_oxdiff_exptl_absorpt_empirical_full_min 0.718