Chiral diene-promoted room temperature conjugate arylation: highly enantioselective synthesis of substituted chiral phenylalanine derivatives and α,α-di(arylmethyl)acetates.
Chen, Jian-Ping; Xu, Ming-Hua; Organic & biomolecular chemistry 18 (2020) 4569–4574; doi:10.1039/d0ob00616e

data_7157426
_publ_section_title
;
 Chiral diene-promoted room temperature conjugate arylation: highly
 enantioselective synthesis of substituted chiral phenylalanine
 derivatives and \a,\a-di(arylmethyl)acetates.
;
_journal_issue                   24
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4569
_journal_page_last               4574
_journal_paper_doi               10.1039/d0ob00616e
_journal_volume                  18
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C25 H29 N O4'
_chemical_formula_sum            'C25 H29 N O4'
_chemical_formula_weight         407.49
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2020-01-15 deposited with the CCDC.	2020-03-26 downloaded from the CCDC.
;
_cell_angle_alpha                99.064(2)
_cell_angle_beta                 98.729(2)
_cell_angle_gamma                91.614(2)
_cell_formula_units_Z            4
_cell_length_a                   9.0309(4)
_cell_length_b                   13.0280(5)
_cell_length_c                   19.9637(8)
_cell_measurement_reflns_used    9929
_cell_measurement_temperature    173
_cell_measurement_theta_max      67.013
_cell_measurement_theta_min      3.441
_cell_volume                     2289.36(16)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.954
_diffrn_measured_fraction_theta_max 0.954
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 0.954
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            27107
_diffrn_reflns_point_group_measured_fraction_full 0.770
_diffrn_reflns_point_group_measured_fraction_max 0.770
_diffrn_reflns_theta_full        62.988
_diffrn_reflns_theta_max         62.988
_diffrn_reflns_theta_min         2.270
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.639
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.5875
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1156 before and 0.0559 after correction. The Ratio of minimum to maximum transmission is 0.7802. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.182
_exptl_crystal_description       block
_exptl_crystal_F_000             872
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.548
_refine_diff_density_min         -0.348
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 3933 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1155
_refine_ls_number_reflns         11398
_refine_ls_number_restraints     1138
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0720
_refine_ls_R_factor_gt           0.0702
_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^)+(0.1780P)^2^+0.2640P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2066
_refine_ls_wR_factor_ref         0.2110
_reflns_Friedel_coverage         0.614
_reflns_Friedel_fraction_full    0.586
_reflns_Friedel_fraction_max     0.586
_reflns_number_gt                10938
_reflns_number_total             11398
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob00616e2.cif
_cod_data_source_block           cu_2017149_0m
_cod_depositor_comments
'Adding full bibliography for 7157426--7157427.cif.'
_cod_database_code               7157426
_shelx_shelxl_version_number     2014/7
_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. Restrained distances
 C64-C63 \\sim C65-C63 \\sim C63-C66 \\sim C63-C67 \\sim C68-C63
 with sigma of 0.02
 C105-C99 \\sim C104-C99 \\sim C103-C99 \\sim C102-C99 \\sim C101-C99 \\sim
C100-C99
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C65) \\sim Ueq, Uanis(C64) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C66) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C100) \\sim Ueq, Uanis(C101) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C103) \\sim Ueq, Uanis(C102) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C105) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C101) \\sim Ueq,
Uanis(C102) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C104) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C79) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C65(0.5) H65A(0.5) H65B(0.5) H65C(0.5) C104(0.5) H10A(0.5)
 H10B(0.5) H10C(0.5) C100(0.5) H10D(0.5) H10E(0.5) H10F(0.5) C66(0.5) H66A(0.5)
 H66B(0.5) H66C(0.5) C103(0.5) H10G(0.5) H10H(0.5) H10I(0.5) C64(0.5) H64A(0.5)
 H64B(0.5) H64C(0.5) C67(0.5) H67A(0.5) H67B(0.5) H67C(0.5) C101(0.5) H10J(0.5)
 H10K(0.5) H10L(0.5) C105(0.5) H10M(0.5) H10N(0.5) H10O(0.5) C102(0.5)
 H10P(0.5) H10Q(0.5) H10R(0.5)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C55(H55), C31(H31), C82(H82)
6.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C56(H56A,H56B), C32(H32A,H32B), C92(H92A,H92B)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C20(H20), C21(H21), C22(H22), C23(H23), C10(H10), C9(H9),
 C59(H59), C75(H75), C74(H74), C58(H58), C76(H76), C62(H62), C73(H73), C61(H61),
  C47(H47), C38(H38), C49(H49), C37(H37), C48(H48), C34(H34), C50(H50),
 C35(H35), C97(H97), C98(H98), C95(H95), C89(H89), C94(H94), C88(H88), C90(H90),
  C87(H87)
6.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C3(H3A,H3B,
 H3C), C2(H2A,H2B,H2C), C1(H1A,H1B,H1C), C53(H53A,H53B,H53C), C52(H52A,H52B,
 H52C), C51(H51A,H51B,H51C), C68(H68A,H68B,H68C), C65(H65A,H65B,H65C), C28(H28A,
 H28B,H28C), C41(H41A,H41B,H41C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C),
 C40(H40A,H40B,H40C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C104(H10A,H10B,
 H10C), C100(H10D,H10E,H10F), C42(H42A,H42B,H42C), C79(H79A,H79B,H79C),
 C66(H66A,H66B,H66C), C103(H10G,H10H,H10I), C64(H64A,H64B,H64C), C67(H67A,H67B,
 H67C), C101(H10J,H10K,H10L), C105(H10M,H10N,H10O), C102(H10P,H10Q,H10R)
;
_olex2_submission_special_instructions 'No special instructions were received'