Palladium-Catalyzed Regioselective Hydroaminocarbonylation of Alkynes to α,β-Unsaturated Primary Amides with Ammonium Chloride.
Ji, Xiaolei; Gao, Bao; Zhou, Xibing; Liu, Zongjian; Huang, Hanmin; The Journal of organic chemistry 83 (2018) 10134–10141; doi:10.1021/acs.joc.8b01405

data_4035053
_publ_section_title
;
 Palladium-Catalyzed Regioselective Hydroaminocarbonylation of Alkynes to
 \a,\b-Unsaturated Primary Amides with Ammonium Chloride.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10134
_journal_page_last               10141
_journal_paper_doi               10.1021/acs.joc.8b01405
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C6 H13 N O Si'
_chemical_formula_sum            'C6 H13 N O Si'
_chemical_formula_weight         143.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-05-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 104.132(11)
_cell_angle_gamma                90.00
_cell_formula_units_Z            20
_cell_length_a                   17.1351(19)
_cell_length_b                   18.0350(11)
_cell_length_c                   15.9634(15)
_cell_measurement_reflns_used    2169
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      22.5220
_cell_measurement_theta_min      3.7260
_cell_volume                     4783.9(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -53.00   -2.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.4273  -57.0000 -180.0000 51

  2 omega  -32.00   73.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -19.0000  -30.0000 105

  3 omega  -35.00   46.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -       22.7867  -57.0000  -90.0000 81
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0286014000
_diffrn_orient_matrix_UB_12      -0.0221082000
_diffrn_orient_matrix_UB_13      -0.0139787000
_diffrn_orient_matrix_UB_21      -0.0301564000
_diffrn_orient_matrix_UB_22      -0.0111655000
_diffrn_orient_matrix_UB_23      -0.0367628000
_diffrn_orient_matrix_UB_31      0.0096723000
_diffrn_orient_matrix_UB_32      0.0305369000
_diffrn_orient_matrix_UB_33      -0.0235909000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0582
_diffrn_reflns_av_unetI/netI     0.1082
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            18641
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.33
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.184
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85641
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.995
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1560
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.638
_refine_diff_density_min         -0.406
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     442
_refine_ls_number_reflns         9396
_refine_ls_number_restraints     82
_refine_ls_restrained_S_all      1.115
_refine_ls_R_factor_all          0.1660
_refine_ls_R_factor_gt           0.0868
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1125P)^2^+1.7327P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2150
_refine_ls_wR_factor_ref         0.2797
_reflns_number_gt                4568
_reflns_number_total             9396
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo8b01405_si_003.cif
_cod_data_source_block           huanghm_0507
_cod_database_code               4035053
_reflns_odcompleteness_completeness 99.72
_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 N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 Si4, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si5, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C29, Si5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Si3, C16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Si4 \\sim C22: within 1.8A with sigma of 0.04 and sigma for terminal atoms of
0.08
Si5 \\sim C28: within 1.8A with sigma of 0.04 and sigma for terminal atoms of
0.08
C29 \\sim Si5: within 1.8A with sigma of 0.04 and sigma for terminal atoms of
0.08
Si3 \\sim C16: within 1.8A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(C29') \\sim Ueq, Uanis(C28') \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.008
Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C16) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(Si4) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.008
4. Others
 Fixed Sof: C28(0.55) H28A(0.55) H28B(0.55) H28C(0.55) C29(0.55) H29A(0.55)
 H29B(0.55) H29C(0.55) C29'(0.45) H29D(0.45) H29E(0.45) H29F(0.45) C28'(0.45)
 H28D(0.45) H28E(0.45) H28F(0.45)
5.a Rotating group:
 N1(H1A,H1B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C8(H8), C9(H9), C14(H14), C15(H15), C20(H20), C21(H21),
 C26(H26), C27(H27)
5.c X=CH2 refined with riding coordinates:
 N2(H2A,H2B), N3(H3A,H3B), N4(H4D,H4E), N5(H5A,H5B)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5C,H5D,H5E), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C29'(H29D,H29E,H29F), C28'(H28D,H28E,H28F)
;
_olex2_date_sample_data_collection 2018-05-07
_olex2_submission_special_instructions 'No special instructions were received'