Enantioselective Decarboxylative Arylation of α-Amino Acids via the Merger of Photoredox and Nickel Catalysis.
Zuo, Zhiwei; Cong, Huan; Li, Wei; Choi, Junwon; Fu, Gregory C.; MacMillan, David W. C.; Journal of the American Chemical Society 138 (2016) 1832–1835; doi:10.1021/jacs.5b13211

data_4124900
_publ_section_title
;
 Enantioselective Decarboxylative Arylation of \a-Amino Acids via the
 Merger of Photoredox and Nickel Catalysis.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              1832
_journal_page_last               1835
_journal_paper_doi               10.1021/jacs.5b13211
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H21 F6 N O2, 0.5(C5 H12)'
_chemical_formula_sum            'C23.5 H27 F6 N O2'
_chemical_formula_weight         469.46
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-13
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.1710(2)
_cell_length_b                   17.9760(6)
_cell_length_c                   24.5859(9)
_cell_measurement_reflns_used    9899
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      69.92
_cell_measurement_theta_min      3.04
_cell_volume                     2285.36(14)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker DUO CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0451
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_laue_measured_fraction_full 1.000
_diffrn_reflns_laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            39031
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.724
_diffrn_reflns_theta_min         3.045
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.033
_exptl_absorpt_correction_T_max  0.7534
_exptl_absorpt_correction_T_min  0.6602
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/4 (Bruker,2014/4) was used for absorption correction. wR2(int) was 0.1006 before and 0.0613 after correction. The Ratio of minimum to maximum transmission is 0.8763. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.364
_exptl_crystal_description       chunk
_exptl_crystal_F_000             980
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 1494 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     440
_refine_ls_number_reflns         4344
_refine_ls_number_restraints     394
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0460
_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^)+(0.0410P)^2^+1.6435P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1056
_refine_ls_wR_factor_ref         0.1094
_reflns_Friedel_coverage         0.698
_reflns_friedel_fraction_full    0.999
_reflns_friedel_fraction_max     0.979
_reflns_number_gt                3955
_reflns_number_total             4344
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b13211_si_001.cif
_cod_data_source_block           crystal01
_cod_depositor_comments          'Adding full bibliography for 4124900.cif.'
_cod_original_formula_sum        'C23.50 H27 F6 N O2'
_cod_database_code               4124900
_shelx_estimated_absorpt_t_max   0.941
_shelx_estimated_absorpt_t_min   0.844
_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. Restrained distances
 C1S-C2S \\sim C2S-C3S \\sim C3S-C4S \\sim C4S-C5S \\sim C1T-C2T \\sim C2T-C3T
\\sim C3T-C4T \\sim C4T-C5T
 \\sim C1U-C2U \\sim C2U-C3U \\sim C3U-C4U \\sim C4U-C5U
 with sigma of 0.02
 C1S-C3S \\sim C2S-C4S \\sim C3S-C5S \\sim C1T-C3T \\sim C2T-C4T \\sim C3T-C5T
\\sim C1U-C3U \\sim C2U-C4U
 \\sim C3U-C5U
 with sigma of 0.02
3. Rigid bond restraints
 C1T, C2T, C3T, C4T, C5T, C1S, C2S, C3S, C4S, C5S, C1U, C2U, C3U, C4U, C5U
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C1T \\sim C2T \\sim C3T \\sim C4T \\sim C5T \\sim C1S \\sim C2S \\sim C3S \\sim
C4S \\sim C5S \\sim C1U \\sim C2U \\sim C3U \\sim C4U \\sim C5U: within 2.4A
with sigma of 0.01 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C10, F4, F4A, F5, F5A, F6, F6A, C10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(C1S)+Sof(H1SA)+Sof(H1SB)+Sof(H1SC)+Sof(C2S)+Sof(H2SA)+Sof(H2SB)+
 Sof(C3S)+Sof(H3SA)+Sof(H3SB)+Sof(C4S)+Sof(H4SA)+Sof(H4SB)+Sof(C5S)+Sof(H5SA)+
 Sof(H5SB)+Sof(H5SC)]+1*[Sof(C1T)+Sof(H1TA)+Sof(H1TB)+Sof(H1TC)+Sof(C2T)+
 Sof(H2TA)+Sof(H2TB)+Sof(C3T)+Sof(H3TA)+Sof(H3TB)+Sof(C4T)+Sof(H4TA)+Sof(H4TB)+
 Sof(C5T)+Sof(H5TA)+Sof(H5TB)+Sof(H5TC)]+1*[Sof(C1U)+Sof(H1UA)+Sof(H1UB)+
 Sof(H1UC)+Sof(C2U)+Sof(H2UA)+Sof(H2UB)+Sof(C3U)+Sof(H3UA)+Sof(H3UB)+Sof(C4U)+
 Sof(H4UA)+Sof(H4UB)+Sof(C5U)+Sof(H5UA)+Sof(H5UB)+Sof(H5UC)]=1 with esd of 0
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=
 Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=
 Sof(H5SC)=0.5*FVAR(3)
 Sof(C1T)=Sof(H1TA)=Sof(H1TB)=Sof(H1TC)=Sof(C2T)=Sof(H2TA)=Sof(H2TB)=Sof(C3T)=
 Sof(H3TA)=Sof(H3TB)=Sof(C4T)=Sof(H4TA)=Sof(H4TB)=Sof(C5T)=Sof(H5TA)=Sof(H5TB)=
 Sof(H5TC)=0.5*FVAR(4)
 Sof(C1U)=Sof(H1UA)=Sof(H1UB)=Sof(H1UC)=Sof(C2U)=Sof(H2UA)=Sof(H2UB)=Sof(C3U)=
 Sof(H3UA)=Sof(H3UB)=Sof(C4U)=Sof(H4UA)=Sof(H4UB)=Sof(C5U)=Sof(H5UA)=Sof(H5UB)=
 Sof(H5UC)=0.5*FVAR(5)
7.a Ternary CH refined with riding coordinates:
 C2(H2)
7.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C2T(H2TA,H2TB), C3T(H3TA,H3TB), C4T(H4TA,H4TB), C2S(H2SA,
 H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C2U(H2UA,H2UB), C3U(H3UA,H3UB),
 C4U(H4UA,H4UB)
7.c Me refined with riding coordinates:
 C1T(H1TA,H1TB,H1TC), C5T(H5TA,H5TB,H5TC), C1S(H1SA,H1SB,H1SC), C5S(H5SA,H5SB,
 H5SC), C1U(H1UA,H1UB,H1UC), C5U(H5UA,H5UB,H5UC)
7.d Aromatic/amide H refined with riding coordinates:
 N1(H1), C4(H4), C6(H6), C8(H8), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17)
7.e Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_shelx_shelxl_version_number     2014/7