Trichloromethyl ketones: asymmetric transfer hydrogenation and subsequent Jocic-type reactions with amines
Michael S. Perryman; Matthew E. Harris; Jade L. Foster; Anushka Joshi; Guy J. Clarkson; David J. Fox; Chem.Commun. 49 (2013) 10022–; doi:10.1039/c3cc46070c

data_7109955
_publ_section_title
;
 Trichloromethyl ketones: asymmetric transfer hydrogenation and subsequent
 Jocic-type reactions with amines
;
_journal_name_full               Chem.Commun.
_journal_page_first              10022
_journal_paper_doi               10.1039/c3cc46070c
_journal_volume                  49
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H23 N2 O, Cl'
_chemical_formula_sum            'C16 H23 Cl N2 O'
_chemical_formula_weight         294.81
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2013-07-25
_audit_creation_method
;
  Olex2 1.2
  (compiled 2013.04.25 svn.r2679, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   4.89752(9)
_cell_length_b                   11.8626(2)
_cell_length_c                   28.4357(6)
_cell_measurement_reflns_used    3453
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      76.9954
_cell_measurement_theta_min      3.1056
_cell_volume                     1652.04(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_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
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.2833
_diffrn_measured_fraction_theta_full 0.9995
_diffrn_measured_fraction_theta_max 0.9947
_diffrn_measurement_details
;
  1 omega  -28.00   32.00   1.0000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6896   19.0000 -120.0000 60

  2 omega -115.00  -11.00   1.0000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6896  -57.0000   90.0000 104

  3 omega  -77.00  -44.00   1.0000   33.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6896   19.0000 -120.0000 33

  4 omega  -48.00   -8.00   1.0000  132.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.5000   30.0000 -150.0000 40

  5 omega   32.00   75.00   1.0000  132.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -94.0000 -180.0000 43

  6 omega   40.00   94.00   1.0000  132.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000 -180.0000 54

  7 omega   60.00   87.00   1.0000  132.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -30.0000  -60.0000 27

  8 omega   41.00   97.00   1.0000  132.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000  -45.0000   60.0000 56

  9 omega   36.00  112.00   1.0000  132.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000 -111.0000 -120.0000 76

 10 omega   29.00  128.00   1.0000  132.0000
omega____ theta____ kappa____ phi______ frames
    -      114.0000    0.0000   30.0000 99
;
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0259779000
_diffrn_orient_matrix_UB_12      -0.1290322000
_diffrn_orient_matrix_UB_13      0.0043717000
_diffrn_orient_matrix_UB_21      0.0579084000
_diffrn_orient_matrix_UB_22      -0.0123067000
_diffrn_orient_matrix_UB_23      -0.0529821000
_diffrn_orient_matrix_UB_31      0.3081286000
_diffrn_orient_matrix_UB_32      -0.0085150000
_diffrn_orient_matrix_UB_33      0.0103370000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0216
_diffrn_reflns_av_unetI/netI     0.0336
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            5719
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.203
_diffrn_reflns_theta_min         3.108
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.020
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72709
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.185
_exptl_crystal_description       block
_exptl_crystal_F_000             632
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1198 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.011(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         3358
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0421
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0499P)^2^+0.3448P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.1033
_reflns_Friedel_coverage         0.667
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.942
_reflns_number_gt                3148
_reflns_number_total             3358
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3cc46070c.txt
_cod_data_source_block           mp2
_cod_original_cell_volume        1652.05(6)
_cod_database_code               7109955
_chemical_oxdiff_formula         'C20 H20 N O2'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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 N(H) groups, All N(H,H) groups
2. Restrained distances
 N11-H11 = N15-H15A = N15-H15B
 0.9 with sigma of 0.008
3.a Ternary CH refined with riding coordinates:
 C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C12(H12A,H12B), C16(H16A,H16B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C13(H13), C17(H17)
3.d X=CH2 refined with riding coordinates:
 C14(H14A,H14B), C18(H18A,H18B)
;
_shelxl_version_number           2013-4