A New Organocatalytic Concept for Asymmetric α-Alkylation of Aldehydes.
Caruana, Lorenzo; Kniep, Florian; Johansen, Tore Kiilerich; Poulsen, Pernille H.; Jørgensen, Karl Anker; Journal of the American Chemical Society  (2014) 141104124641007–; doi:10.1021/ja510475n

data_4122891
_publ_section_title
;
 A New Organocatalytic Concept for Asymmetric \a-Alkylation of Aldehydes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141104124641007
_journal_paper_doi               10.1021/ja510475n
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C32 H39 Br O3'
_chemical_formula_sum            'C32 H39 Br O3'
_chemical_formula_weight         551.57
_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_Int_Tables_number      4
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-18
_audit_creation_method
;
Olex2 1.2
(compiled 2014.06.20 svn.r2946 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.827(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.5080(6)
_cell_length_b                   9.0189(4)
_cell_length_c                   20.0580(8)
_cell_measurement_reflns_used    3050
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      17.7080
_cell_measurement_theta_min      2.4820
_cell_volume                     2886.9(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2013)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3590
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9995
_diffrn_measured_fraction_theta_max 0.9995
_diffrn_measurement_details
;
  1 omega  -20.00   77.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803  -99.0000    0.0000 97

  2 omega   35.00  128.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803  178.0000  -30.0000 93

  3 omega  -42.00   -6.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803  131.0000   61.7559 36

  4 omega  -64.00   71.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803  -38.0000  120.0000 135

  5 omega  -17.00  127.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803   77.0000 -120.0000 144

  6 omega -120.00   14.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -      -27.8741  -57.0000   90.0000 134

  7 omega  -65.00   68.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803  -57.0000   30.0000 133

  8 omega  -20.00   77.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803  -99.0000  -30.0000 97

  9 omega  -15.00   10.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803   57.0000  150.0000 25

 10 omega  -15.00  119.00   1.0000   29.0000
omega____ theta____ kappa____ phi______ frames
    -       26.7803   57.0000   30.0000 134
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0227058000
_diffrn_orient_matrix_UB_12      0.0167508000
_diffrn_orient_matrix_UB_13      0.0246680000
_diffrn_orient_matrix_UB_21      0.0378444000
_diffrn_orient_matrix_UB_22      0.0202817000
_diffrn_orient_matrix_UB_23      0.0241104000
_diffrn_orient_matrix_UB_31      -0.0051971000
_diffrn_orient_matrix_UB_32      0.0741176000
_diffrn_orient_matrix_UB_33      -0.0121859000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1298
_diffrn_reflns_av_unetI/netI     0.0976
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            31301
_diffrn_reflns_theta_full        26.0000
_diffrn_reflns_theta_max         20.82
_diffrn_reflns_theta_min         1.85
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.453
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84448
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.2689
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1159.3524
_exptl_crystal_size_max          0.1093
_exptl_crystal_size_mid          0.0659
_exptl_crystal_size_min          0.0427
_refine_diff_density_max         0.5796
_refine_diff_density_min         -0.4999
_refine_diff_density_rms         0.1044
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   -0.025(15)
_refine_ls_d_res_high            1.0000
_refine_ls_d_res_low             11.0160
_refine_ls_goodness_of_fit_ref   1.0644
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    124
_refine_ls_number_parameters     664
_refine_ls_number_reflns         6034
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0644
_refine_ls_R_factor_all          0.0974
_refine_ls_R_factor_gt           0.0565
_refine_ls_shift/su_max          0.0008
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0517P)^2^+0.6160P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1144
_refine_ls_wR_factor_ref         0.1350
_reflns_Friedel_coverage         1.000
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              9
_reflns_limit_k_min              -9
_reflns_limit_l_max              20
_reflns_limit_l_min              -19
_reflns_number_gt                4295
_reflns_number_total             6034
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            ja510475n_si_002.cif
_cod_data_source_block           exp_2283
_cod_database_code               4122891
_chemical_oxdiff_formula         'C32 H39 Br O3'
_reflns_odcompleteness_completeness 99.95
_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, All O(H) groups
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Ternary CH refined with riding coordinates:
 C16(H16), C21(H21), C48(H48), C89(H89)
3.b Secondary CH2 refined with riding coordinates:
 C22(H22a,H22b), C34(H34a,H34b), C35(H35a,H35b), C1A(H1Aa,H1Ab)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C8(H8), C9(H9), C10(H10), C11(H11), C24(H24), C26(H26), C52(H52),
 C55(H55), C59(H59), C61(H61), C63(H63), C67(H67), C68(H68), C71(H71), C87(H87),
  C4(H4), C15(H15a), C19(H19), C1C(H1C), C1F(H1F), C1G(H1G)
3.d Idealised Me refined as rotating group:
 C27(H27a,H27b,H27c), C28(H28a,H28b,H28c), C51(H51a,H51b,H51c), C81(H81a,H81b,
 H81c), C102(H10d,H10e,H10f), C105(H10a,H10b,H10c), C5(H5a,H5b,H5c), C1E(H1Ea,
 H1Eb,H1Ec), C1H(H1Ha,H1Hb,H1Hc), C1J(H1Ja,H1Jb,H1Jc), C1K(H1Ka,H1Kb,H1Kc),
 C1L(H1La,H1Lb,H1Lc), C1M(H1Ma,H1Mb,H1Mc), C1N(H1Na,H1Nb,H1Nc)
3.e Idealised tetrahedral OH refined as rotating group:
 O15(H15), O1(H1a)
;
_olex2_submission_special_instructions 'No special instructions were received'