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_7109956
_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         'C24 H24 Cl2 N2 O'
_chemical_formula_sum            'C24 H24 Cl2 N2 O'
_chemical_formula_weight         427.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2013-07-29
_audit_creation_method
;
  Olex2 1.2
  (compiled 2013.04.25 svn.r2679, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.0265(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.83139(7)
_cell_length_b                   12.10798(10)
_cell_length_c                   18.33461(15)
_cell_measurement_reflns_used    10736
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      77.7989
_cell_measurement_theta_min      3.6475
_cell_volume                     2174.13(3)
_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    'SUPERFLIP, J. Appl. Cryst. (2007) 40, 786-790'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 10.2833
_diffrn_measured_fraction_theta_full 0.9998
_diffrn_measured_fraction_theta_max 0.9977
_diffrn_measurement_details
;
  1 omega  -85.00   49.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532    0.0000   30.0000 134

  2 omega    9.00   35.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532   38.0000  120.0000 26

  3 omega   10.00   35.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532   38.0000   90.0000 25

  4 omega  -49.00    7.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6532   38.0000   90.0000 56

  5 omega   41.00   89.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       40.6532 -125.0000 -150.0000 48

  6 omega    7.00   76.00   1.0000   13.0000
omega____ theta____ kappa____ phi______ frames
    -       40.6532   77.0000   60.0000 69

  7 omega  -54.00  -28.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      -61.5000   45.0000   60.0000 26

  8 omega  -53.00    7.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      -61.5000   45.0000  120.0000 60

  9 omega  -23.00    3.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      -61.5000   30.0000 -180.0000 26

 10 omega   43.00   76.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000 -111.0000 -120.0000 33

 11 omega   51.00  129.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -77.0000   30.0000 78

 12 omega   37.00   88.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -30.0000  150.0000 51

 13 omega   44.00   78.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -45.0000 -120.0000 34

 14 omega   88.00  178.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   45.0000  -90.0000 90

 15 omega   68.00  169.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000   15.0000    0.0000 101

 16 omega   37.00   63.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000 -113.0000   32.0000 26

 17 omega   43.00   79.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -45.0000  -90.0000 36

 18 omega   51.00  109.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -94.0000 -180.0000 58

 19 omega   39.00   86.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -30.0000  -30.0000 47

 20 omega   40.00   76.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -45.0000 -150.0000 36

 21 omega   41.00   93.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -45.0000   30.0000 52

 22 omega   39.00   90.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -30.0000   90.0000 51

 23 omega   75.00  108.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -94.0000 -120.0000 33

 24 omega   71.00  131.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000  -77.0000  -90.0000 60

 25 omega   88.00  115.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000 -111.0000 -120.0000 27

 26 omega   87.00  112.00   1.0000   52.0000
omega____ theta____ kappa____ phi______ frames
    -      115.0000 -113.0000   32.0000 25
;
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0133745000
_diffrn_orient_matrix_UB_12      -0.0246083000
_diffrn_orient_matrix_UB_13      0.0815016000
_diffrn_orient_matrix_UB_21      0.0321462000
_diffrn_orient_matrix_UB_22      -0.1225843000
_diffrn_orient_matrix_UB_23      -0.0130317000
_diffrn_orient_matrix_UB_31      0.1533967000
_diffrn_orient_matrix_UB_32      0.0235041000
_diffrn_orient_matrix_UB_33      0.0174785000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0249
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            16749
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.021
_diffrn_reflns_theta_min         4.381
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.816
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75384
_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    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.498
_refine_diff_density_min         -0.460
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 3940 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).

From Shelxl 2013-4
Flack x =   0.022(14) by hole-in-one fit to all intensities
            0.023(10) from 3940 selected quotients (Parsons' method)
From Olex 2 
Hooft y parameter 0.025(4)
;
_refine_ls_abs_structure_Flack   0.023(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     535
_refine_ls_number_reflns         8992
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0871P)^2^+0.5715P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1302
_refine_ls_wR_factor_ref         0.1322
_reflns_Friedel_coverage         0.872
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.943
_reflns_number_gt                8712
_reflns_number_total             8992
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3cc46070c.txt
_cod_data_source_block           mp3
_cod_database_code               7109956
_reflns_odcompleteness_completeness 99.98
_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
2. Restrained distances
 N119-H119
 0.98 with sigma of 0.02
3. Same fragment restrains
{N119, N219}
as
{Cl1, Cl2}
4.a Ternary CH refined with riding coordinates:
 C109(H109), C209(H209)
4.b Secondary CH2 refined with riding coordinates:
 C107(H10A,H10B), C108(H10C,H10D), C112(H11A,H11B), C120(H12A,H12B), C207(H20A,
 H20B), C208(H20C,H20D), C212(H21A,H21B), C220(H22A,H22B)
4.c Aromatic/amide H refined with riding coordinates:
 C101(H101), C102(H102), C103(H103), C104(H104), C105(H105), C114(H114),
 C115(H115), C117(H117), C118(H118), C122(H122), C123(H123), C125(H125),
 C126(H126), C201(H201), C202(H202), C203(H203), C204(H204), C205(H205),
 C214(H214), C215(H215), C217(H217), C218(H218), C222(H222), C223(H223),
 C225(H225), C226(H226)
;
_shelxl_version_number           2013-4