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_7109954
_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 unk
_chemical_formula_moiety         'C18 H30 N2 O'
_chemical_formula_sum            'C18 H30 N2 O'
_chemical_formula_weight         290.44
_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             2013-07-03
_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                   6.17114(12)
_cell_length_b                   12.3956(2)
_cell_length_c                   24.5886(4)
_cell_measurement_reflns_used    10237
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      77.8730
_cell_measurement_theta_min      3.5627
_cell_volume                     1880.90(6)
_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
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      120.15
_diffrn_detector_area_resol_mean 10.2833
_diffrn_measured_fraction_theta_full 0.9995
_diffrn_measured_fraction_theta_max 0.9955
_diffrn_measurement_details
;
  1 omega -123.00   -5.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.6268  -77.0000 -150.0000 118

  2 omega  -59.00  -11.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.6268  -38.0000 -120.0000 48

  3 omega  -95.00  -50.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.6268  125.0000  150.0000 45

  4 omega   30.00   83.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.6268  -99.0000  120.0000 53

  5 omega   36.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       39.6268 -125.0000   60.0000 55

  6 omega  -58.00  -32.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -78.0000  -96.3007 26

  7 omega  -64.00  -32.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -77.0000  -60.0000 32

  8 omega -147.00  -81.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -77.0000  -60.0000 66

  9 omega  -68.00  -32.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -77.0000 -150.0000 36

 10 omega  -54.00   10.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000   45.0000 -120.0000 64

 11 omega -152.00 -122.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -78.0000  -96.3007 30

 12 omega -105.00  -78.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -77.0000 -150.0000 27

 13 omega -114.00  -83.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -78.0000  -96.3007 31

 14 omega  -62.00  -34.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -77.0000 -180.0000 28

 15 omega  -62.00  -35.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -77.0000 -120.0000 27

 16 omega -151.00  -50.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -68.5000  -76.0000  161.8281 101

 17 omega   85.00  155.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   61.0000  -30.0000 70

 18 omega   43.00   95.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -45.0000 -180.0000 52

 19 omega   85.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   61.0000  -60.0000 26

 20 omega   85.00  116.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   61.0000  -90.0000 31

 21 omega  112.00  177.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   77.0000  -90.0000 65

 22 omega   51.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000  150.0000 60

 23 omega   40.00   98.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -45.0000    0.0000 58

 24 omega   82.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   77.0000  -60.0000 26

 25 omega  119.00  155.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   77.0000  -60.0000 36

 26 omega   83.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   77.0000 -120.0000 26

 27 omega   85.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   61.0000 -150.0000 27

 28 omega   86.00  111.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   61.0000 -180.0000 25

 29 omega  127.00  153.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   61.0000 -180.0000 26

 30 omega   82.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   77.0000  -90.0000 26

 31 omega   86.00  178.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   61.0000 -120.0000 92

 32 omega   89.00  116.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   45.0000  -60.0000 27

 33 omega   87.00  128.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   45.0000 -120.0000 41

 34 omega   37.00   97.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000    0.0000 60

 35 omega   88.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   45.0000  -90.0000 27

 36 omega   88.00  171.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   45.0000 -150.0000 83

 37 omega   82.00  108.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   77.0000 -180.0000 26

 38 omega   83.00  109.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   77.0000 -150.0000 26

 39 omega   37.00   89.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -30.0000  -60.0000 52

 40 omega   80.00  106.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000  -90.0000 26

 41 omega   39.00   64.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -30.0000 -150.0000 25
;
_diffrn_measurement_device_type  'Xcalibur, Ruby, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0086253000
_diffrn_orient_matrix_UB_12      0.1240768000
_diffrn_orient_matrix_UB_13      0.0029819000
_diffrn_orient_matrix_UB_21      -0.0536132000
_diffrn_orient_matrix_UB_22      -0.0066772000
_diffrn_orient_matrix_UB_23      0.0610837000
_diffrn_orient_matrix_UB_31      0.2437058000
_diffrn_orient_matrix_UB_32      0.0029526000
_diffrn_orient_matrix_UB_33      0.0135445000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0482
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            16534
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         66.592
_diffrn_reflns_theta_min         3.595
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.487
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70536
_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    1.026
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.207
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.048
_refine_ls_abs_structure_details
;
 Flack x determined using 1359 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
 Flack x =   0.076(743) by hole-in-one fit to all intensities (Shelxl)
             0.038(128) from 1359 selected quotients (Parsons' method)
Hooft y parameter 0.20(10)(Olex2)

Not able to determine the absolute configuration form the Flack or Hooft y
(only one oxygen in the molecule!)
;
_refine_ls_abs_structure_Flack   -0.04(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.202
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         3324
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.201
_refine_ls_R_factor_all          0.0615
_refine_ls_R_factor_gt           0.0613
_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^)+(0.0508P)^2^+1.3078P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1607
_refine_ls_wR_factor_ref         0.1608
_reflns_Friedel_coverage         0.709
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3304
_reflns_number_total             3324
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c3cc46070c.txt
_cod_data_source_block           mp1
_cod_original_cell_volume        1880.91(6)
_cod_database_code               7109954
_chemical_oxdiff_formula         'C20 H20 N2 O2'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H211 of N211, H111 of N111, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H216 of N216, H116 of N116
2. Restrained distances
 N116-H116 = N216-H216
 1.03 with sigma of 0.02
 C209-H216 = C217-H216
 2.1 with sigma of 0.04
3. Others
 Sof(C201)=Sof(H201)=Sof(C202)=Sof(H202)=Sof(C203)=Sof(H203)=Sof(C204)=
 Sof(H204)=Sof(C205)=Sof(H205)=Sof(C206)=Sof(C207)=Sof(H20A)=Sof(H20B)=
 Sof(C208)=Sof(H20C)=Sof(H20D)=Sof(C209)=Sof(H209)=Sof(C210)=Sof(O210)=
 Sof(N211)=Sof(H211)=Sof(C212)=Sof(C213)=Sof(H21A)=Sof(H21B)=Sof(H21C)=
 Sof(C214)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C215)=Sof(H21G)=Sof(H21H)=
 Sof(H21I)=Sof(N216)=Sof(H216)=Sof(C217)=Sof(C218)=Sof(H21J)=Sof(H21K)=
 Sof(H21L)=Sof(C219)=Sof(H21M)=Sof(H21N)=Sof(H21O)=Sof(C220)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=1-FVAR(1)
 Sof(C101)=Sof(H101)=Sof(C102)=Sof(H102)=Sof(C103)=Sof(H103)=Sof(C104)=
 Sof(H104)=Sof(C105)=Sof(H105)=Sof(C106)=Sof(C107)=Sof(H10A)=Sof(H10B)=
 Sof(C108)=Sof(H10C)=Sof(H10D)=Sof(C109)=Sof(H109)=Sof(C110)=Sof(O110)=
 Sof(N111)=Sof(H111)=Sof(C112)=Sof(C113)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C114)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C115)=Sof(H11G)=Sof(H11H)=
 Sof(H11I)=Sof(N116)=Sof(H116)=Sof(C117)=Sof(C118)=Sof(H11J)=Sof(H11K)=
 Sof(H11L)=Sof(C119)=Sof(H11M)=Sof(H11N)=Sof(H11O)=Sof(C120)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=FVAR(1)
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), C207(H20A,H20B), C208(H20C,H20D)
4.c Me refined with riding coordinates:
 C214(H21D,H21E,H21F)
4.d Aromatic/amide H refined with riding coordinates:
 C101(H101), C102(H102), C103(H103), C104(H104), C105(H105), N111(H111),
 C201(H201), C202(H202), C203(H203), C204(H204), C205(H205), N211(H211)
4.e Idealised Me refined as rotating group:
 C113(H11A,H11B,H11C), C114(H11D,H11E,H11F), C115(H11G,H11H,H11I), C118(H11J,
 H11K,H11L), C119(H11M,H11N,H11O), C120(H12A,H12B,H12C), C213(H21A,H21B,H21C),
 C215(H21G,H21H,H21I), C218(H21J,H21K,H21L), C219(H21M,H21N,H21O), C220(H22A,
 H22B,H22C)
;
_shelxl_version_number           2013-2