One-pot catalytic asymmetric borylation of unsaturated aldehyde-derived imines; functionalisation to homoallylic boronate carboxylate ester derivatives.
Pujol, Alba; Calow, Adam D. J.; Batsanov, Andrei S.; Whiting, Andrew; Organic & biomolecular chemistry 13 (2015) 5122–5130; doi:10.1039/c4ob02657h

data_7154385
_publ_section_title
;
 One-pot catalytic asymmetric borylation of unsaturated aldehyde-derived
 imines; functionalisation to homoallylic boronate carboxylate ester
 derivatives.
;
_journal_issue                   18
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5122
_journal_page_last               5130
_journal_paper_doi               10.1039/c4ob02657h
_journal_volume                  13
_journal_year                    2015
_chemical_formula_moiety         'C20 H17 N S'
_chemical_formula_sum            'C20 H17 N S'
_chemical_formula_weight         303.40
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-10-30
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.10.28 svn.r3060 for OlexSys, GUI svn.r4931)
;
_audit_update_record
;
2014-12-21 deposited with the CCDC.
2015-03-24 downloaded from the CCDC.
;
_cell_angle_alpha                99.3522(19)
_cell_angle_beta                 98.9080(19)
_cell_angle_gamma                101.371(2)
_cell_formula_units_Z            2
_cell_length_a                   6.04042(15)
_cell_length_b                   11.6602(3)
_cell_length_c                   12.1628(2)
_cell_measurement_reflns_used    5194
_cell_measurement_temperature    120
_cell_measurement_theta_max      29.8030
_cell_measurement_theta_min      1.8030
_cell_volume                     813.07(3)
_computing_cell_refinement
; CrysAlisPro, Agilent Technologies, Version 1.171.37.31 
(release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
; CrysAlisPro, Agilent Technologies, Version 1.171.37.31 
(release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
; CrysAlisPro, Agilent Technologies, Version 1.171.37.31 
(release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement
'SHELXL 2014/7 multi-CPU version (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.15
_diffrn_detector_type            'Sapphire3 CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.872
_diffrn_measurement_details
;
  1 omega  -24.00   21.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5469 -100.0000  -90.0000 150

  2 omega  -24.00   60.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       20.3282 -100.0000 -120.0000 280

  3 omega    2.00   89.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       20.3282   57.0000  120.0000 290

  4 omega    2.00   89.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       20.3282   57.0000   30.0000 290

  5 omega  -51.00   91.20   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       20.3282    0.0000 -150.0000 474

  6 omega   32.00   95.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       20.3282 -178.0000 -150.0000 210

  7 omega  -24.00   21.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.5469 -100.0000  120.0000 150

  8 omega   -2.00   91.00   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       20.3282   38.0000    0.0000 310

  9 omega    5.00   46.40   0.3000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       20.3282 -137.0000   72.5717 138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Agilent Technologies, Gemini S Ultra kappa-diffractometer'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0110576000
_diffrn_orient_matrix_UB_12      -0.0567012000
_diffrn_orient_matrix_UB_13      0.0110418000
_diffrn_orient_matrix_UB_21      -0.1192601000
_diffrn_orient_matrix_UB_22      -0.0232051000
_diffrn_orient_matrix_UB_23      -0.0217895000
_diffrn_orient_matrix_UB_31      0.0236098000
_diffrn_orient_matrix_UB_32      -0.0159932000
_diffrn_orient_matrix_UB_33      -0.0550626000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0281
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.872
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12662
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.872
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.352
_diffrn_reflns_theta_min         2.246
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.195
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.927
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
; CrysAlisPro, Agilent Technologies, Version 1.171.37.31 
(release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 
2014,18:38:05) Analytical numeric absorption correction 
using a multifaceted crystal model based on expressions 
derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, 
J. S. (1995). Acta Cryst. A51, 887-897)
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.239
_exptl_crystal_description       irregular
_exptl_crystal_F_000             320
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.5195
_exptl_crystal_size_mid          0.3634
_exptl_crystal_size_min          0.1745
_refine_diff_density_max         0.479
_refine_diff_density_min         -0.326
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         4269
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0460P)^2^+0.3740P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1033
_refine_ls_wR_factor_ref         0.1085
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3829
_reflns_number_total             4269
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4ob02657h2.cif
_cod_data_source_block           2j
_cod_depositor_comments
'Adding full bibliography for 7154381--7154385.cif.'
_cod_database_code               7154385
_chemical_oxdiff_formula         'C20 H17 N S'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Shared sites
{S, C6'}
{S', C6}
3. Uiso/Uaniso restraints and constraints
Uanis(S) = Uanis(C6')
Uanis(S') = Uanis(C6)
4. Others
 Fixed Sof: S(0.8) C6'(0.2) H6'(0.2) C6(0.8) H6(0.8) S'(0.2)
5.a Riding coordinates:
 C6(H6), C7(H7), C8(H8)
5.b Ternary CH refined with riding coordinates:
 C1(H1)
5.c Aromatic/amide H refined with riding coordinates:
 C6'(H6'), C2(H2), C3(H3), C4(H4), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
;
_shelx_shelxl_version_number     2014/7
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_submission_special_instructions 'No special instructions were received'