Ultrafast amidation of esters using lithium amides under aerobic ambient temperature conditions in sustainable solvents.
Fairley, Michael; Bole, Leonie J.; Mulks, Florian F.; Main, Laura; Kennedy, Alan R.; O'Hara, Charles T; García-Alvarez, Joaquín; Hevia, Eva; Chemical science 11 (2020) 6500–6509; doi:10.1039/d0sc01349h

data_1557969
_publ_section_title
;
 Ultrafast amidation of esters using lithium amides under aerobic ambient
 temperature conditions in sustainable solvents.
;
_journal_issue                   25
_journal_name_full               'Chemical science'
_journal_page_first              6500
_journal_page_last               6509
_journal_paper_doi               10.1039/d0sc01349h
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety
'C39 H50 Li2 N2 O3, 0.72(C5 H10 O), 0.28(C5 H7 O)'
_chemical_formula_sum            'C44 H60 Li2 N2 O4'
_chemical_formula_weight         694.82
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_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             2019-06-13
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-12-20 deposited with the CCDC.	2020-04-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.453(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.2268(4)
_cell_length_b                   19.0435(7)
_cell_length_c                   10.7658(5)
_cell_measurement_reflns_used    7467
_cell_measurement_temperature    123.35(10)
_cell_measurement_theta_max      72.9960
_cell_measurement_theta_min      4.2000
_cell_volume                     2047.36(15)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.35(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0268
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
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omega____ theta____ kappa____ phi______ frames
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  2 omega   -4.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
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  3 omega   -4.00   42.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000   30.0000 46

  4 omega   18.00  113.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000 -125.0000 -120.0000 95

  5 omega  -14.00   86.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
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  6 omega   30.00  128.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   37.0000 -120.0000 98

  7 omega  -13.00   77.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -57.0000  -30.0000 90

  8 omega  -16.00   82.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000  -37.0000 -150.0000 98

  9 omega   30.00  128.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   37.0000  150.0000 98

 10 omega  100.00  178.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000 -150.0000 78

 11 omega  100.00  178.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000 -180.0000 78

 12 omega   40.00  116.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000  -60.0000 76

 13 omega  100.00  178.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  111.0000  120.0000 78

 14 omega   39.00   94.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000  -30.0000 55

 15 omega   40.00  116.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000 -111.0000 -180.0000 76

 16 omega   44.00  134.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -63.0000 -180.0000 90

 17 omega   40.00   92.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -37.0000   90.0000 52

 18 omega   44.00  134.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
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 19 omega   39.00   94.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
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 20 omega   39.00   94.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -25.0000  -60.0000 55

 21 omega   40.00  150.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -91.0000 -150.0000 110

 22 omega   90.00  178.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000   63.0000 -180.0000 88

 23 omega   40.00  150.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
    -      112.0000  -91.0000   30.0000 110

 24 omega   78.00  178.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
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 25 omega   39.00   94.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
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 26 omega   39.00   94.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
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 27 omega   40.00  116.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
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 28 omega   90.00  178.00   1.0000    9.0000
omega____ theta____ kappa____ phi______ frames
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 29 omega  -21.00   69.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
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 30 omega  -73.00   44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
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 31 omega   35.00  125.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000    0.0000 90

 32 omega   35.00  125.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   57.0000   60.0000 90

 33 omega   26.00  126.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   77.0000  -90.0000 100
;
_diffrn_measurement_device       'four-circle diffractometer'
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_diffrn_orient_matrix_UB_11      0.0790191000
_diffrn_orient_matrix_UB_12      -0.0110342000
_diffrn_orient_matrix_UB_13      0.1374912000
_diffrn_orient_matrix_UB_21      0.0678254000
_diffrn_orient_matrix_UB_22      0.0719356000
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_diffrn_orient_matrix_UB_31      -0.1138959000
_diffrn_orient_matrix_UB_32      0.0352776000
_diffrn_orient_matrix_UB_33      0.0505109000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0775
_diffrn_reflns_av_unetI/netI     0.0562
_diffrn_reflns_Laue_measured_fraction_full 1.000
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_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -19
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_diffrn_reflns_number            23108
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_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.996
_diffrn_reflns_theta_min         4.205
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.544
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_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
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_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.723
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 2150 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.3(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.225
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     542
_refine_ls_number_reflns         7090
_refine_ls_number_restraints     252
_refine_ls_restrained_S_all      1.254
_refine_ls_R_factor_all          0.1080
_refine_ls_R_factor_gt           0.0987
_refine_ls_shift/su_max          0.000
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_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2735
_refine_ls_wR_factor_ref         0.2948
_reflns_Friedel_coverage         0.772
_reflns_Friedel_fraction_full    0.837
_reflns_Friedel_fraction_max     0.823
_reflns_number_gt                6096
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_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc01349h2.cif
_cod_data_source_block           mf7
_cod_depositor_comments
;Adding full bibliography for 1557967--1557970.cif.

 Adding full bibliography for 1557967--1557970.cif.
;
_cod_original_cell_volume        2047.35(15)
_cod_database_code               1557969
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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
 O1-C28 = O1-C25 = O4-C40 = O4-C43 = O2-C33 = O2-C30 = O3-C35 = O3-C38
 1.43 with sigma of 0.01
 O2-C33A = O2-C30A = O1-C25A = O1-C28A = O3-C35A = O3-C38A
 1.43 with sigma of 0.01
 O4A-C40A = O4A-C43A
 1.43 with sigma of 0.01
 C40-C41 = C41-C42 = C42-C43 = C43-C44
 1.53 with sigma of 0.01
 C28-C27 = C27-C26 = C26-C25 = C25-C29
 1.53 with sigma of 0.01
 C35-C36 = C36-C37 = C37-C38 = C38-C39
 1.53 with sigma of 0.01
 C33-C32 = C32-C31 = C31-C30 = C30-C34
 1.53 with sigma of 0.01
 C33A-C32A = C32A-C31A = C31A-C30A = C30A-C34A
 1.53 with sigma of 0.01
 C28A-C27A = C27A-C26A = C26A-C25A = C25A-C29A
 1.53 with sigma of 0.01
 C30A-C33A = C33A-C31A
 2.3 with sigma of 0.02
 C35A-C36A = C36A-C37A = C37A-C38A = C38A-C39A
 1.53 with sigma of 0.01
 C40A-C41A = C41A-C42A = C42A-C43A = C43A-C44A
 1.53 with sigma of 0.01
 C25A-C27A
 2.3 with sigma of 0.02
 C35A-C37A
 2.3 with sigma of 0.02
 C35A-C38A
 2.3 with sigma of 0.02
 O4A-C42A
 2.35 with sigma of 0.02
 C26A-C28A
 2.3 with sigma of 0.02
3. Rigid bond restraints
 O4, C40, C41, C42, C43, C44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O3, C35, C36, C37, C38, C39
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O2, C30, C31, C32, C33, C34
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1, C25, C26, C27, C28, C29
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O4 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.02
O3 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.02
O2 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.02
O1 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29: within 1.7A with sigma of
0.02 and sigma for terminal atoms of 0.02
Uanis(C33) = Uanis(C33A)
Uanis(C32) = Uanis(C32A)
Uanis(C31) = Uanis(C31A)
Uanis(C30) = Uanis(C30A)
Uanis(C34) = Uanis(C34A)
Uanis(C28) = Uanis(C28A)
Uanis(C27) = Uanis(C27A)
Uanis(C26) = Uanis(C26A)
Uanis(C25) = Uanis(C25A)
Uanis(C29) = Uanis(C29A)
Uanis(C35) = Uanis(C35A)
Uanis(C36) = Uanis(C36A)
Uanis(C37) = Uanis(C37A)
Uanis(C38) = Uanis(C38A)
Uanis(C39) = Uanis(C39A)
Uanis(O4) = Uanis(O4A)
Uanis(C44) = Uanis(C44A)
Uanis(C43) = Uanis(C43A)
Uanis(C42) = Uanis(C42A)
Uanis(C40) = Uanis(C40A)
Uanis(C41) = Uanis(C41A)
5. Others
 Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=
 Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C25A)=Sof(H25A)=Sof(C27A)=Sof(H27C)=
 Sof(H27D)=1-FVAR(1)
 Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(1)
 Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31C)=Sof(H31D)=Sof(C32A)=Sof(H32C)=
 Sof(H32D)=Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34D)=Sof(H34E)=
 Sof(H34F)=1-FVAR(2)
 Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(2)
 Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C37A)=
 Sof(H37C)=Sof(H37D)=Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39D)=Sof(H39E)=
 Sof(H39F)=1-FVAR(3)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=
 Sof(H37B)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(3)
 Sof(O4A)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(C42A)=Sof(H42C)=
 Sof(H42D)=Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=Sof(C43A)=1-FVAR(4)
 Sof(O4)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=
 FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C25(H25), C30(H30), C38(H38), C43(H43), C30A(H30A), C25A(H25A), C38A(H38A)
6.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C31(H31A,H31B), C32(H32A,
 H32B), C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B),
 C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C31A(H31C,H31D), C32A(H32C,
 H32D), C33A(H33C,H33D), C28A(H28C,H28D), C26A(H26C,H26D), C27A(H27C,H27D),
 C35A(H35C,H35D), C36A(H36C,H36D), C37A(H37C,H37D), C40A(H40C,H40D), C42A(H42C,
 H42D)
6.c Me refined with riding coordinates:
 C34A(H34D,H34E,H34F), C44A(H44D,H44E,H44F)
6.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24)
6.e Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C34(H34A,H34B,H34C), C39(H39A,H39B,H39C), C44(H44A,H44B,
 H44C), C29A(H29D,H29E,H29F), C39A(H39D,H39E,H39F)
;
_shelx_res_checksum              89118
_olex2_submission_special_instructions 'No special instructions were received'