Regioselective 1,4- over 1,2-addition of 3,3-bis(silyl) allyloxy lithium to enals, enones and enoates. The remarkable α-effect of silicon.
Ye, Xincui; Sun, Xianwei; Huang, Zhenggang; Yang, Na; Su, Zhishan; Hu, Changwei; Song, Zhenlei; Organic & biomolecular chemistry 12 (2014) 3021–3025; doi:10.1039/c4ob00139g

data_7153757
_publ_section_title
;
 Regioselective 1,4- over 1,2-addition of 3,3-bis(silyl) allyloxy lithium
 to enals, enones and enoates. The remarkable \a-effect of silicon.
;
_journal_issue                   19
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              3021
_journal_page_last               3025
_journal_paper_doi               10.1039/c4ob00139g
_journal_volume                  12
_journal_year                    2014
_chemical_formula_moiety         'C35 H48 N4 O12 Si2'
_chemical_formula_sum            'C35 H48 N4 O12 Si2'
_chemical_formula_weight         772.95
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-09-15
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                81.100(8)
_cell_angle_beta                 84.633(8)
_cell_angle_gamma                87.844(8)
_cell_formula_units_Z            2
_cell_length_a                   8.2957(8)
_cell_length_b                   9.7941(10)
_cell_length_c                   27.385(3)
_cell_measurement_reflns_used    3218
_cell_measurement_temperature    294.04(10)
_cell_measurement_theta_max      24.5360
_cell_measurement_theta_min      3.4110
_cell_volume                     2188.0(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      294.04(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9982
_diffrn_measured_fraction_theta_max 0.8844
_diffrn_measurement_details
;
  1 omega   -9.00   22.50   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -99.0000 -120.0000 21

  2 omega -102.00  -55.50   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000    0.0000 31

  3 omega   12.00   49.50   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700   57.0000   90.0000 25

  4 omega  -45.00   46.50   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -57.0000 -180.0000 61

  5 omega   -3.00   93.00   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000  -30.0000 64

  6 omega    5.00   32.00   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000 -150.0000 18

  7 omega   -1.00   92.00   1.5000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000   60.0000 62
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0253302000
_diffrn_orient_matrix_UB_12      0.0653364000
_diffrn_orient_matrix_UB_13      0.0041223000
_diffrn_orient_matrix_UB_21      -0.0123638000
_diffrn_orient_matrix_UB_22      0.0280147000
_diffrn_orient_matrix_UB_23      -0.0248845000
_diffrn_orient_matrix_UB_31      -0.0811630000
_diffrn_orient_matrix_UB_32      0.0179411000
_diffrn_orient_matrix_UB_33      0.0075280000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_av_unetI/netI     0.0707
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            16639
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.500
_diffrn_reflns_theta_max         28.49
_diffrn_reflns_theta_min         3.01
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.139
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58420
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.173
_exptl_crystal_F_000             820
_refine_diff_density_max         0.408
_refine_diff_density_min         -0.441
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     484
_refine_ls_number_reflns         8603
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.1169
_refine_ls_R_factor_gt           0.0748
_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^)+(0.1285P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2098
_refine_ls_wR_factor_ref         0.2439
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4863
_reflns_number_total             8603
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4ob00139g2.cif
_cod_data_source_block           songzhl0913_2
_cod_database_code               7153757
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C8(H8), C10(H10), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C24(H24A,H24B),
 C26(H26A,H26B), C28(H28A,H28B), C30(H30A,H30B), C32(H32A,H32B), C34(H34A,H34B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C17(H17), C19(H19), C21(H21), C22(H22)
2.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C31(H31A,H31B,
 H31C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C)
;
_shelx_hkl_checksum              85394
_shelx_res_checksum              50561
_shelxl_version_number           2013-2