Synthesis of Amides with Remote Stereocenters by Catalytic Asymmetric γ-Alkynylation of α,β-Unsaturated Amides.
Wang, Zi-Xuan; Bai, Xiao-Yan; Yao, Han-Chao; Li, Bi-Jie; Journal of the American Chemical Society 138 (2016) 14872–14875; doi:10.1021/jacs.6b10415

data_4131167
_publ_section_title
;
 Synthesis of Amides with Remote Stereocenters by Catalytic Asymmetric
 \g-Alkynylation of \a,\b-Unsaturated Amides.
;
_journal_issue                   45
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14872
_journal_page_last               14875
_journal_paper_doi               10.1021/jacs.6b10415
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H20 Br N O'
_chemical_formula_sum            'C20 H20 Br N O'
_chemical_formula_weight         370.28
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-13
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.116(9)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.336(6)
_cell_length_b                   5.059(3)
_cell_length_c                   19.254(12)
_cell_measurement_reflns_used    2840
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4051
_cell_measurement_theta_min      2.1560
_cell_volume                     892.3(10)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution
;
'SHELXT (Sheldrick, 2014)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 10.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 90.0000
	             XTD: 45.2613
	          2theta: -20.0926
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 10.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 270.0000
	             XTD: 45.2613
	          2theta: -20.0926
scan:
	Number of images: 360
	           Slice: -110.0000 - 70.0000
	     Image width: 0.5000
	        Exp time: 10.0000
	   Rotation axis: Omega
	           Omega: 0.0000
	             Chi: 45.0000
	             Phi: 0.0000
	             XTD: 45.2613
	          2theta: -20.0926
;
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Saturn724+ CCD'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      0.0054
_diffrn_orient_matrix_UB_12      0.1072
_diffrn_orient_matrix_UB_13      -0.0198
_diffrn_orient_matrix_UB_21      -0.1940
_diffrn_orient_matrix_UB_22      0.0027
_diffrn_orient_matrix_UB_23      -0.0379
_diffrn_orient_matrix_UB_31      -0.0092
_diffrn_orient_matrix_UB_32      0.0198
_diffrn_orient_matrix_UB_33      0.0482
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Graphite Monochromator'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0525
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10531
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.420
_diffrn_reflns_theta_min         2.223
_diffrn_source                   'Sealed Tube'
_diffrn_source_current           30.0000
_diffrn_source_power             1.5000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.307
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70266
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.378
_exptl_crystal_description       needle
_exptl_crystal_F_000             380
_exptl_crystal_size_max          0.625
_exptl_crystal_size_mid          0.072
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.302
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 994 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.155
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         4021
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.155
_refine_ls_R_factor_all          0.0684
_refine_ls_R_factor_gt           0.0575
_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^)+(0.0173P)^2^+0.5410P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0920
_refine_ls_wR_factor_ref         0.0969
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    0.980
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                3495
_reflns_number_total             4021
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b10415_si_002.cif
_cod_data_source_block           alkynyl-amide
_cod_original_cell_volume        892.4(10)
_cod_database_code               4131167
_diffrn_number_total             2266
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1A)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C12(H12A,H12B), C13(H13A,H13B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C7(H7), C8(H8), C10(H10), C11(H11), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20)
2.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C)
;
_shelx_res_checksum              33688
_shelx_hkl_checksum              99901
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'