Enantioselective Copper-Catalyzed Reductive Coupling of Alkenylazaarenes with Ketones
Aakarsh Saxena; Bonnie Choi; Hon Wai Lam; Journal of the American Chemical Society 134 (2012) 8428–8431; doi:10.1021/ja3036916

data_4117978
_publ_contact_author_email       S.Parsons@ed.ac.uk
_publ_contact_author_name        'Simon Parsons'
_publ_section_title
;
 Enantioselective Copper-Catalyzed Reductive Coupling of Alkenylazaarenes
 with Ketones
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8428
_journal_page_last               8431
_journal_paper_doi               10.1021/ja3036916
_journal_volume                  134
_journal_year                    2012
_chemical_absolute_configuration ad
_chemical_compound_source        'Aakarsh Saxena and Hon Lam sample BC77E'
_chemical_formula_moiety         'C17 H19 F1 N2 O2'
_chemical_formula_sum            'C17 H19 F N2 O2'
_chemical_formula_weight         302.35
_space_group_IT_number           19
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     'Charge flipping'
_audit_creation_date             12-03-28
_audit_creation_method           CRYSTALS_ver_14.23
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.57390(10)
_cell_length_b                   13.18190(10)
_cell_length_c                   18.67780(10)
_cell_measurement_reflns_used    47228
_cell_measurement_temperature    150
_cell_measurement_theta_max      74
_cell_measurement_theta_min      3
_cell_volume                     1618.55(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_molecular_graphics    XP
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_diffrn_ambient_temperature      150
_diffrn_detector_area_resol_mean 10.3147
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       omega
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_source         'SuperNova (Cu) X-ray Source'
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.024
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            64078
_diffrn_reflns_theta_full        73.968
_diffrn_reflns_theta_max         73.968
_diffrn_reflns_theta_min         4.105
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.740
_exptl_absorpt_correction_T_max  0.93
_exptl_absorpt_correction_T_min  0.83
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   Crysalis
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.241
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_recrystallization_method
;
from EtOAc and n-hexane.
;
_exptl_crystal_size_max          0.215
_exptl_crystal_size_mid          0.179
_exptl_crystal_size_min          0.095
_refine_diff_density_max         0.13
_refine_diff_density_min         -0.09
_refine_ls_abs_structure_details 'Flack (1983), 3279 Friedel-pairs'
_refine_ls_abs_structure_Flack   0.03(7)
_refine_ls_extinction_coef       36(5)
_refine_ls_extinction_method     'Larson (1970), Equation 22'
_refine_ls_goodness_of_fit_ref   0.9967
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     277
_refine_ls_number_reflns         3233
_refine_ls_number_restraints     103
_refine_ls_R_factor_all          0.0233
_refine_ls_R_factor_gt           0.0230
_refine_ls_shift/su_max          0.0009722
_refine_ls_shift/su_mean         0.0000684
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 Method= 
 SQRT(W) = 1/(Data with the key SIGMA(/FO/) in list 6) 
;
_refine_ls_weighting_scheme      sigma
_refine_ls_wR_factor_all         0.0456
_refine_ls_wR_factor_gt          0.0455
_refine_ls_wR_factor_ref         0.0456
_reflns_limit_h_max              8
_reflns_limit_h_min              -8
_reflns_limit_k_max              16
_reflns_limit_k_min              0
_reflns_limit_l_max              23
_reflns_limit_l_min              0
_reflns_number_gt                3199
_reflns_number_total             3279
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   0.00
_oxford_diffrn_Wilson_scale      0.00
_oxford_refine_ls_r_factor_ref   0.0233
_oxford_refine_ls_scale          2.194(11)
_oxford_reflns_number_all        3233
_oxford_reflns_threshold_expression_ref I>-10.0\s(I)
_oxford_structure_analysis_title 'hl2009 in P2(1)2(1)2(1)'
_cod_data_source_file            ja3036916_si_007.cif
_cod_data_source_block           hl2009
_cod_original_sg_symbol_H-M      'P 21 21 21 '
_cod_original_formula_sum        'C17 H19 F1 N2 O2'
_cod_database_code               4117978
_iucr_refine_instruction_details_constraints
;
BLOCK 
CONT SCALE 
CONT F    (    1 ,X'S,U'S)  UNTIL C    (   20 ) 
CONT H    (    2 ,X'S,U[ISO])  UNTIL H    (  203 ) 
CONT EXTPARAM 
CONT ENANTIO 
END                                                                             
;
_iucr_refine_instruction_details_restraints
;
NO 
REM   HREST   START (DO NOT REMOVE THIS LINE) 
REM NO H   NO #H U MULT DIST 
REM C-H 
REM >4           1.5    .96 DISORDER 
REM 1      1     1.2    .93 C C-H (ACETYLENE) 
REM 1      2     1.2    .93 C-C(H)-C 
REM 1      3     1.2    .98 (C)3-C-H 
REM 2      1     1.2    .93 C=C-H(2) 
REM 2      2     1.2    .97 (C)2-C-(H)2 
REM 3      1     1.5    .96 C-C-(H)3 
REM N-H 
REM >4           1.5    .89 DISORDER 
REM 1      1     1.2    .86 N-N/H 
REM 1      2     1.2    .86 (C)2-N-H 
REM 1      3     1.2    .89 (C)3-N-H 
REM 2      1     1.2    .86 C-N-(H)2 
REM 2      2     1.2    .89 (C)2-N-(H)2 
REM 3      1     1.2    .89 C-H-(H)3 
REM O-H 
REM 1      1     1.5    .82 O-H 
REM 
REM DIST      ESD = 0.02 
REM VIB       ESD = 0.002 
REM ANGLE     ESD = 2.0 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 2) TO H(2) 
REST 0.040, 0.002 = H(2,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(2) TO C ( 2) TO C(1) 
CONT H(2) TO C ( 2) TO C(3) 
PLANAR C ( 2) C(1) C(3) H(2) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 5) TO H(5) 
REST 0.036, 0.002 = H(5,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(5) TO C ( 5) TO C(4) 
CONT H(5) TO C ( 5) TO C(6) 
PLANAR C ( 5) C(4) C(6) H(5) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 6) TO H(6) 
REST 0.040, 0.002 = H(6,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(6) TO C ( 6) TO C(5) 
CONT H(6) TO C ( 6) TO C(1) 
PLANAR C ( 6) C(5) C(1) H(6) 
REM            2 H ON SP 3 
DIST 0.97, 0.02 = 
CONT C ( 7) TO H(71) 
CONT C ( 7) TO H(72) 
REST 0.044, 0.002 = H(71,U[ISO]) 
REST 0.044, 0.002 = H(72,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(71) TO C ( 7) TO C(3) 
CONT H(71) TO C ( 7) TO C(8) 
CONT H(72) TO C ( 7) TO C(3) 
CONT H(72) TO C ( 7) TO C(8) 
ANGLE 109.54, 2.0 = 
CONT H(71) TO C ( 7) TO H(72) 
REM            2 H ON SP 3 
DIST 0.97, 0.02 = 
CONT C ( 8) TO H(81) 
CONT C ( 8) TO H(82) 
REST 0.038, 0.002 = H(81,U[ISO]) 
REST 0.038, 0.002 = H(82,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(81) TO C ( 8) TO C(7) 
CONT H(81) TO C ( 8) TO C(9) 
CONT H(82) TO C ( 8) TO C(7) 
CONT H(82) TO C ( 8) TO C(9) 
ANGLE 109.54, 2.0 = 
CONT H(81) TO C ( 8) TO H(82) 
REM       H ON O-HETRO ATOM 
DIST 0.82, 0.02 = 
CONT O ( 9) TO H(9) 
REST 0.044, 0.002 = H(9,U[ISO]) 
REM            1 H ON SP 3 
DIST 0.98, 0.02 = 
CONT C ( 10) TO H(10) 
REST 0.029, 0.002 = H(10,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(10) TO C ( 10) TO C(9) 
CONT H(10) TO C ( 10) TO C(11) 
CONT H(10) TO C ( 10) TO C(17) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 13) TO H(13) 
REST 0.043, 0.002 = H(13,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(13) TO C ( 13) TO N(12) 
CONT H(13) TO C ( 13) TO C(14) 
PLANAR C ( 13) N(12) C(14) H(13) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 14) TO H(14) 
REST 0.044, 0.002 = H(14,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(14) TO C ( 14) TO C(13) 
CONT H(14) TO C ( 14) TO C(15) 
PLANAR C ( 14) C(13) C(15) H(14) 
REM            1 H ON SP 2 
DIST 0.93, 0.02 = 
CONT C ( 15) TO H(15) 
REST 0.045, 0.002 = H(15,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(15) TO C ( 15) TO C(14) 
CONT H(15) TO C ( 15) TO N(16) 
PLANAR C ( 15) C(14) N(16) H(15) 
REM            2 H ON SP 3 
DIST 0.97, 0.02 = 
CONT C ( 17) TO H(171) 
CONT C ( 17) TO H(172) 
REST 0.035, 0.002 = H(171,U[ISO]) 
REST 0.035, 0.002 = H(172,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(171) TO C ( 17) TO C(10) 
CONT H(171) TO C ( 17) TO C(18) 
CONT H(172) TO C ( 17) TO C(10) 
CONT H(172) TO C ( 17) TO C(18) 
ANGLE 109.54, 2.0 = 
CONT H(171) TO C ( 17) TO H(172) 
REM            2 H ON SP 3 
DIST 0.97, 0.02 = 
CONT C ( 18) TO H(181) 
CONT C ( 18) TO H(182) 
REST 0.040, 0.002 = H(181,U[ISO]) 
REST 0.040, 0.002 = H(182,U[ISO]) 
ANGLE 0.0, 2.0 = MEAN 
CONT H(181) TO C ( 18) TO C(17) 
CONT H(181) TO C ( 18) TO O(19) 
CONT H(182) TO C ( 18) TO C(17) 
CONT H(182) TO C ( 18) TO O(19) 
ANGLE 109.54, 2.0 = 
CONT H(181) TO C ( 18) TO H(182) 
REM            3 H ON SP 3 
DIST 0.96, 0.02 = 
CONT C ( 20) TO H(201) 
CONT C ( 20) TO H(202) 
CONT C ( 20) TO H(203) 
REST 0.068, 0.002 = H(201,U[ISO]) 
REST 0.068, 0.002 = H(202,U[ISO]) 
REST 0.068, 0.002 = H(203,U[ISO]) 
ANGLE 109.54, 2.0 = 
CONT O(19) TO C ( 20) TO H(201) 
CONT O(19) TO C ( 20) TO H(202) 
CONT O(19) TO C ( 20) TO H(203) 
ANGLE 0.0, 2.0 = MEAN H(201) TO C ( 20) TO H(202) 
CONT H(201) TO C ( 20) TO H(203) 
CONT H(202) TO C ( 20) TO H(203) 
REM   HREST   END (DO NOT REMOVE THIS LINE) 
END                                                                             
;