Organocatalyzed Asymmetric Oxidative Coupling of α-Csp(3)-H of Tertiary Amines to α,β-Unsaturated γ-Butyrolactam: Synthesis of MBH-Type Products.
Ma, Yunxia; Zhang, Gen; Zhang, Jinlong; Yang, Dongxu; Wang, Rui; Organic letters 16 (2014) 5358–5361; doi:10.1021/ol5025597

data_1517848
_publ_section_title
;
 Organocatalyzed Asymmetric Oxidative Coupling of \a-Csp(3)-H of Tertiary
 Amines to \a,\b-Unsaturated \g-Butyrolactam: Synthesis of MBH-Type
 Products.
;
_journal_issue                   20
_journal_name_full               'Organic letters'
_journal_page_first              5358
_journal_page_last               5361
_journal_paper_doi               10.1021/ol5025597
_journal_volume                  16
_journal_year                    2014
_chemical_absolute_configuration none
_chemical_formula_moiety         '0.5(C27 H32 N2 O5), 0.5(C27 H30 N2 O5)'
_chemical_formula_sum            'C27 H31 N2 O5'
_chemical_formula_weight         463.54
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_symmetry_space_group_name_Hall  'P 65'
_symmetry_space_group_name_H-M   'P 65'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-04-11
_audit_creation_method
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Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
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_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            12
_cell_length_a                   38.5889(17)
_cell_length_b                   38.5889(17)
_cell_length_c                   6.4839(3)
_cell_measurement_reflns_used    4364
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      66.2070
_cell_measurement_theta_min      4.7560
_cell_volume                     8361.6(6)
_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
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
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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, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0453847000
_diffrn_orient_matrix_UB_12      0.0163719000
_diffrn_orient_matrix_UB_13      -0.0175827000
_diffrn_orient_matrix_UB_21      -0.0078614000
_diffrn_orient_matrix_UB_22      -0.0422746000
_diffrn_orient_matrix_UB_23      -0.0525862000
_diffrn_orient_matrix_UB_31      -0.0016859000
_diffrn_orient_matrix_UB_32      0.0083565000
_diffrn_orient_matrix_UB_33      -0.2310131000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
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_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -46
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_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       5
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            20463
_diffrn_reflns_point_group_measured_fraction_full 0.718
_diffrn_reflns_point_group_measured_fraction_max 0.682
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.501
_diffrn_reflns_theta_min         3.499
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.619
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41663
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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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 yellow'
_exptl_crystal_density_diffrn    1.105
_exptl_crystal_description       block
_exptl_crystal_F_000             2964
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.545
_refine_diff_density_min         -0.274
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 1311 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.02(15)
_refine_ls_extinction_coef       0.0010(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     626
_refine_ls_number_reflns         7524
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1060
_refine_ls_R_factor_gt           0.0898
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1887P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2453
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_reflns_Friedel_coverage         0.296
_reflns_Friedel_fraction_full    0.377
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_reflns_number_gt                5369
_reflns_number_total             7524
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol5025597_si_002.cif
_cod_data_source_block           mayx0409_cu
_cod_depositor_comments          'Adding full bibliography for 1517848.cif.'
_cod_original_cell_volume        8361.6(8)
_cod_database_code               1517848
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
2. Uiso/Uaniso restraints and constraints
Uanis(C32) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(N3) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C15(H15), C42(H42)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C21(H21A,H21B), C48(H48A,H48B)
3.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C10(H10), C13(H13), C20(H20), C28(H28),
 C29(H29), C31(H31), C32(H32), C34(H34), C35(H35), C37(H37), C40(H40), C49(H49)
3.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C43(H43A,H43B,H43C), C44(H44A,
 H44B,H44C), C45(H45A,H45B,H45C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C)
;
_shelx_res_checksum              26980
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