Tunable reactivity of geminal bis(silyl) enol derivatives leading to selective exo-IEDDA or Sakurai allylation with a β,γ-unsaturated ketoester.
Gan, Zubao; Chu, Zhiwen; Hu, Jia; Su, Zhishan; Hu, Changwei; Gao, Lu; Song, Zhenlei; Chemical communications (Cambridge, England) 52 (2016) 10137–10140; doi:10.1039/c6cc04593f

data_7124779
_publ_section_title
;
 Tunable reactivity of geminal bis(silyl) enol derivatives leading to
 selective exo-IEDDA or Sakurai allylation with a \b,\g-unsaturated
 ketoester.
;
_journal_issue                   66
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10137
_journal_page_last               10140
_journal_paper_doi               10.1039/c6cc04593f
_journal_volume                  52
_journal_year                    2016
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C48 H69 N O6 Si2'
_chemical_formula_sum            'C48 H69 N O6 Si2'
_chemical_formula_weight         812.22
_chemical_melting_point          83.0(10)
_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   geom
_audit_creation_date             2016-05-12
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-05-19 deposited with the CCDC.
2016-07-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.50766(19)
_cell_length_b                   14.7380(2)
_cell_length_c                   35.4339(6)
_cell_measurement_reflns_used    7297
_cell_measurement_temperature    293
_cell_measurement_theta_max      72.3980
_cell_measurement_theta_min      4.1960
_cell_volume                     5487.36(15)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega   10.00  104.00   1.0000    5.6850
omega____ theta____ kappa____ phi______ frames
    -       36.5421   77.0000  -90.0000 94

  2 omega  -31.00   63.00   1.0000    5.6850
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -77.0000 -120.0000 94

  3 omega   23.00   79.00   1.0000    5.6850
omega____ theta____ kappa____ phi______ frames
    -       36.5421 -125.0000 -150.0000 56

  4 omega   11.00   75.00   1.0000    5.6850
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -99.0000   60.0000 64

  5 omega  -33.00   21.00   1.0000    5.6850
omega____ theta____ kappa____ phi______ frames
    -       36.5421  -38.0000  -30.0000 54

  6 omega   50.00   96.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   60.0000 46

  7 omega   44.00   89.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 45

  8 omega   44.00   71.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 27

  9 omega   44.00   70.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -90.0000 26

 10 omega   47.00   90.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   30.0000 43

 11 omega   54.00   89.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 35

 12 omega   49.00   78.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 29

 13 omega  104.00  160.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   60.0000 56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0612273000
_diffrn_orient_matrix_UB_12      0.0121052000
_diffrn_orient_matrix_UB_13      -0.0391706000
_diffrn_orient_matrix_UB_21      -0.0867509000
_diffrn_orient_matrix_UB_22      0.0823352000
_diffrn_orient_matrix_UB_23      -0.0075360000
_diffrn_orient_matrix_UB_31      0.1009693000
_diffrn_orient_matrix_UB_32      0.0633668000
_diffrn_orient_matrix_UB_33      0.0172867000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0260
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            16011
_diffrn_reflns_point_group_measured_fraction_full 0.862
_diffrn_reflns_point_group_measured_fraction_max 0.862
_diffrn_reflns_theta_full        67.055
_diffrn_reflns_theta_max         67.055
_diffrn_reflns_theta_min         4.389
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.896
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35103
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    0.983
_exptl_crystal_F_000             1760
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.265
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 2545 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     523
_refine_ls_number_reflns         8477
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0589
_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^)+(0.1212P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1553
_refine_ls_wR_factor_ref         0.1607
_reflns_Friedel_coverage         0.549
_reflns_Friedel_fraction_full    0.691
_reflns_Friedel_fraction_max     0.691
_reflns_number_gt                7744
_reflns_number_total             8477
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc04593f2.cif
_cod_data_source_block           liubo-gan-d-98-p_sq
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '82-84' was changed to
'83.0(10)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_original_cell_volume        5487.38(16)
_cod_database_code               7124779
_reflns_odcompleteness_completeness 99.84
_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
2.a Ternary CH refined with riding coordinates:
 C007(H007), C008(H008), C009(H009), C00G(H00G), C00J(H00J), C00K(H00K),
 C016(H016)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00A,H00B), C00R(H00C,H00D), C00S(H00F,H00H), C00V(H00I,H00M), C00X(H00P,
 H00R), C00Y(H00S,H00V), C00Z(H00W,H00X), C010(H01A,H01B), C018(H01F,H01G),
 C01A(H01H,H01I)
2.c Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00L(H00L), C00N(H00N), C00O(H00O), C00Q(H00Q), C00T(H00T),
 C00U(H00U), C011(H011), C013(H013), C015(H015), C017(H017), C019(H019),
 C01E(H01S), C01F(H01T), C01G(H01U)
2.d Idealised Me refined as rotating group:
 C012(H01C,H01D,H01E), C01B(H01J,H01K,H01L), C01C(H01M,H01N,H01O), C01D(H01P,
 H01Q,H01R), C01H(H01V,H01W,H01X), C01I(H01Y,H,HA), C01J(H01Z,HB,HC), C01K(H01,
 HD,HE), C01L(H0AA,HF,HG)
;
_shelx_res_checksum              32904
_shelx_fab_checksum              68963
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2015-07-08
_olex2_submission_special_instructions 'No special instructions were received'