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_7153756
_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         'C38 H48 N4 O12 Si2'
_chemical_formula_sum            'C38 H48 N4 O12 Si2'
_chemical_formula_weight         808.98
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-09-04
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_cell_angle_alpha                83.291(8)
_cell_angle_beta                 72.695(9)
_cell_angle_gamma                73.531(9)
_cell_formula_units_Z            2
_cell_length_a                   10.9442(10)
_cell_length_b                   12.2254(12)
_cell_length_c                   17.0170(17)
_cell_measurement_reflns_used    3708
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.9350
_cell_measurement_theta_min      3.4300
_cell_volume                     2083.3(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      293(2)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.9975
_diffrn_measured_fraction_theta_max 0.8780
_diffrn_measurement_details
;
  1 omega -103.00  -55.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  178.0000   30.0000 32

  2 omega  -70.00  -43.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -38.0000  120.0000 18

  3 omega  -19.00   27.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.3700  -99.0000 -120.0000 31

  4 omega   75.00  105.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  178.0000   90.0000 20

  5 omega   47.00   90.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  178.0000  -90.0000 29

  6 omega  -30.00   40.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -57.0000 -150.0000 47

  7 omega   14.00   93.50   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512   57.0000   90.0000 53

  8 omega  -49.00   71.00   1.5000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       22.6512  -19.0000  -90.0000 80
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0001942000
_diffrn_orient_matrix_UB_12      0.0497795000
_diffrn_orient_matrix_UB_13      -0.0260058000
_diffrn_orient_matrix_UB_21      -0.0363734000
_diffrn_orient_matrix_UB_22      0.0343709000
_diffrn_orient_matrix_UB_23      0.0344798000
_diffrn_orient_matrix_UB_31      0.0602133000
_diffrn_orient_matrix_UB_32      0.0023693000
_diffrn_orient_matrix_UB_33      0.0065787000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_reflns_av_R_equivalents  0.0723
_diffrn_reflns_av_unetI/netI     0.1394
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            15746
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         2.99
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.149
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79778
_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_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             856
_exptl_crystal_size_max          0.4100
_exptl_crystal_size_mid          0.1700
_exptl_crystal_size_min          0.1400
_refine_diff_density_max         0.550
_refine_diff_density_min         -0.370
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.943
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     511
_refine_ls_number_reflns         8178
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      0.958
_refine_ls_R_factor_all          0.1519
_refine_ls_R_factor_gt           0.0709
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0514P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1429
_refine_ls_wR_factor_ref         0.1871
_reflns_number_gt                3559
_reflns_number_total             8178
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c4ob00139g2.cif
_cod_data_source_block           songzhl0903
_cod_original_cell_volume        2083.3(3)
_cod_database_code               7153756
_reflns_odcompleteness_completeness 99.75
_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. Uiso/Uaniso restraints and constraints
Uanis(C38) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C3(H3), C4(H4)
3.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C27(H27A,H27B), C29(H29A,H29B), C31(H31A,H31B),
 C33(H33A,H33B), C35(H35A,H35B), C37(H37A,H37B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C15(H15), C17(H17),
 C19(H19), C22(H22), C24(H24), C26(H26)
3.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C34(H34A,H34B,
 H34C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C)
;