Copper-Catalyzed Umpolung of Imines through Carbon-to-Nitrogen Boryl Migration

We report a general strategy for the catalytic umpolung of imines, which was enabled by an unprecedented 1,2-boryl carbon-to-nitrogen migration. Based on the discovery of a rearrangement of an α-borylalkylamido copper intermediate to an α-borylaminoalkyl copper species through 1,2-migration of a bor...

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Published inACS catalysis Vol. 9; no. 5; pp. 4388 - 4393
Main Authors Li, Zhenghua, Zhang, Liang, Nishiura, Masayoshi, Hou, Zhaomin
Format Journal Article
LanguageEnglish
Published American Chemical Society 03.05.2019
Subjects
copper catalysis
amine synthesis
imine umpolung
allylation
boryl migration
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Abstract We report a general strategy for the catalytic umpolung of imines, which was enabled by an unprecedented 1,2-boryl carbon-to-nitrogen migration. Based on the discovery of a rearrangement of an α-borylalkylamido copper intermediate to an α-borylaminoalkyl copper species through 1,2-migration of a boryl group from carbon to nitrogen and copper migration from nitrogen to carbon, we have developed a copper-catalyzed selective allylation of a wide range of aldimines and ketimines with allyl electrophiles in the presence of B2(pin)2 and LiOtBu. We expect this catalytic imine-umpolung strategy may derive useful methodologies for the synthesis of various functionalized amines.
AbstractList We report a general strategy for the catalytic umpolung of imines, which was enabled by an unprecedented 1,2-boryl carbon-to-nitrogen migration. Based on the discovery of a rearrangement of an α-borylalkylamido copper intermediate to an α-borylaminoalkyl copper species through 1,2-migration of a boryl group from carbon to nitrogen and copper migration from nitrogen to carbon, we have developed a copper-catalyzed selective allylation of a wide range of aldimines and ketimines with allyl electrophiles in the presence of B2(pin)2 and LiOtBu. We expect this catalytic imine-umpolung strategy may derive useful methodologies for the synthesis of various functionalized amines.
Author Hou, Zhaomin
Zhang, Liang
Li, Zhenghua
Nishiura, Masayoshi
AuthorAffiliation Advanced Catalysis Research Group
Organometallic Chemistry Laboratory
RIKEN Cluster for Pioneering Research
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  givenname: Masayoshi
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  surname: Nishiura
  fullname: Nishiura, Masayoshi
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  givenname: Zhaomin
  orcidid: 0000-0003-2841-5120
  surname: Hou
  fullname: Hou, Zhaomin
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  organization: RIKEN Cluster for Pioneering Research
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Cites_doi 10.1021/jacs.6b09754
10.1039/c3sc53526f
10.1039/C4CC06156J
10.1021/ja063671r
10.1021/ja306771n
10.1055/s-0034-1380187
10.1002/anie.201506872
10.1002/anie.201806874
10.1021/jo4000477
10.1002/anie.201710915
10.1021/acs.chemrev.6b00193
10.1002/adsc.201600075
10.1016/S0040-4020(00)01089-9
10.1002/anie.201607918
10.1073/pnas.1718474115
10.1021/ol500522d
10.1021/jo952116x
10.1002/anie.201509757
10.1039/c2cc00020b
10.1021/acs.orglett.7b04055
10.1021/ar50075a003
10.1039/C6CC09654A
10.1016/j.tet.2009.02.034
10.1039/C5SC01589H
10.1021/ja402569j
10.1002/anie.197902393
10.1021/ja3063474
10.1021/ol502043j
10.1021/jo500300t
10.1021/ol502693r
10.1021/ja909909q
10.1021/acs.orglett.8b02536
10.1021/acs.joc.8b02893
10.1021/jacs.7b01373
10.1021/ja203138q
10.1021/ol8012765
10.1021/ja800829y
10.1021/ja501560x
10.1021/acs.orglett.8b00778
10.1002/anie.201602278
10.1021/acs.orglett.5b00107
10.1038/s41467-018-07351-2
10.1021/acs.orglett.5b01954
10.1038/nchem.2760
10.1021/ol802070d
10.1021/jm501100b
10.1002/chem.201201425
10.1021/acs.joc.5b00255
10.1038/nature14617
10.1021/ja0566679
10.1002/anie.201611268
10.1038/523417a
10.1021/acs.orglett.8b03394
10.1039/b903098k
10.1021/jacs.6b00283
10.1021/jacs.6b05288
10.1002/anie.201812585
10.1021/ol071080f
10.1021/ja047708o
10.1021/ja063115x
10.1021/acs.orglett.5b00934
10.1055/s-0032-1318145
10.1002/9783527629541
10.1021/ol902651j
10.1021/jo035245j
10.1002/anie.201607813
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Keywords copper catalysis
amine synthesis
imine umpolung
allylation
boryl migration
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References ref12/cit12h
ref5/cit5v
ref12/cit12g
ref12/cit12f
ref5/cit5t
ref12/cit12e
ref5/cit5u
ref12/cit12d
ref12/cit12c
ref12/cit12b
ref12/cit12a
ref2/cit2b
ref2/cit2a
ref5/cit5b
ref5/cit5c
ref5/cit5a
ref11/cit11g
ref11/cit11f
ref11/cit11c
ref11/cit11b
ref11/cit11e
ref3/cit3a
ref11/cit11d
ref5/cit5r
ref5/cit5s
ref5/cit5p
ref11/cit11a
ref5/cit5q
ref13/cit13
ref5/cit5n
ref7/cit7c
ref5/cit5o
ref7/cit7b
ref5/cit5l
ref7/cit7a
ref5/cit5m
ref5/cit5j
ref5/cit5k
ref5/cit5h
ref5/cit5i
ref5/cit5f
ref5/cit5g
ref5/cit5d
ref5/cit5e
ref9/cit9c
ref9/cit9b
ref9/cit9a
ref8/cit8a
ref10/cit10a
ref10/cit10b
ref8/cit8b
Nugent T. C. (ref3/cit3b) 2010
ref9/cit9d
ref6/cit6d
ref4/cit4a
ref6/cit6e
ref4/cit4b
ref6/cit6f
ref6/cit6g
ref14/cit14a
ref14/cit14c
ref14/cit14b
ref6/cit6a
ref1/cit1
ref6/cit6b
ref6/cit6c
References_xml – ident: ref5/cit5d
  doi: 10.1021/jacs.6b09754
– ident: ref5/cit5r
  doi: 10.1039/c3sc53526f
– ident: ref5/cit5q
  doi: 10.1039/C4CC06156J
– ident: ref14/cit14b
  doi: 10.1021/ja063671r
– ident: ref5/cit5u
  doi: 10.1021/ja306771n
– ident: ref12/cit12e
  doi: 10.1055/s-0034-1380187
– ident: ref2/cit2b
  doi: 10.1002/anie.201506872
– ident: ref9/cit9d
  doi: 10.1002/anie.201806874
– ident: ref11/cit11f
  doi: 10.1021/jo4000477
– ident: ref5/cit5e
  doi: 10.1002/anie.201710915
– ident: ref13/cit13
  doi: 10.1021/acs.chemrev.6b00193
– ident: ref5/cit5k
  doi: 10.1002/adsc.201600075
– ident: ref12/cit12b
  doi: 10.1016/S0040-4020(00)01089-9
– ident: ref5/cit5c
  doi: 10.1002/anie.201607918
– ident: ref5/cit5g
  doi: 10.1073/pnas.1718474115
– ident: ref5/cit5i
  doi: 10.1021/ol500522d
– ident: ref12/cit12c
  doi: 10.1021/jo952116x
– ident: ref5/cit5s
  doi: 10.1002/anie.201509757
– ident: ref11/cit11c
  doi: 10.1039/c2cc00020b
– ident: ref7/cit7c
  doi: 10.1021/acs.orglett.7b04055
– ident: ref12/cit12a
  doi: 10.1021/ar50075a003
– ident: ref6/cit6b
  doi: 10.1039/C6CC09654A
– ident: ref5/cit5o
  doi: 10.1016/j.tet.2009.02.034
– ident: ref5/cit5t
  doi: 10.1039/C5SC01589H
– ident: ref11/cit11d
  doi: 10.1021/ja402569j
– ident: ref1/cit1
  doi: 10.1002/anie.197902393
– ident: ref10/cit10a
  doi: 10.1021/ja3063474
– ident: ref5/cit5j
  doi: 10.1021/ol502043j
– ident: ref11/cit11b
  doi: 10.1021/jo500300t
– ident: ref6/cit6g
  doi: 10.1021/ol502693r
– ident: ref5/cit5p
  doi: 10.1021/ja909909q
– ident: ref6/cit6c
  doi: 10.1021/acs.orglett.8b02536
– ident: ref5/cit5l
  doi: 10.1021/acs.joc.8b02893
– ident: ref8/cit8b
  doi: 10.1021/jacs.7b01373
– ident: ref5/cit5v
  doi: 10.1021/ja203138q
– ident: ref4/cit4b
  doi: 10.1021/ol8012765
– ident: ref11/cit11a
  doi: 10.1021/ja800829y
– ident: ref5/cit5b
  doi: 10.1021/ja501560x
– ident: ref9/cit9a
  doi: 10.1021/acs.orglett.8b00778
– ident: ref10/cit10b
  doi: 10.1002/anie.201602278
– ident: ref5/cit5n
  doi: 10.1021/acs.orglett.5b00107
– ident: ref9/cit9c
  doi: 10.1038/s41467-018-07351-2
– ident: ref12/cit12g
  doi: 10.1021/acs.orglett.5b01954
– ident: ref5/cit5f
  doi: 10.1038/nchem.2760
– ident: ref5/cit5h
  doi: 10.1021/ol802070d
– ident: ref3/cit3a
  doi: 10.1021/jm501100b
– ident: ref6/cit6f
  doi: 10.1002/chem.201201425
– ident: ref12/cit12f
  doi: 10.1021/acs.joc.5b00255
– ident: ref5/cit5a
  doi: 10.1038/nature14617
– ident: ref14/cit14a
  doi: 10.1021/ja0566679
– ident: ref7/cit7a
  doi: 10.1002/anie.201611268
– ident: ref2/cit2a
  doi: 10.1038/523417a
– ident: ref9/cit9b
  doi: 10.1021/acs.orglett.8b03394
– ident: ref14/cit14c
  doi: 10.1039/b903098k
– ident: ref12/cit12h
  doi: 10.1021/jacs.6b00283
– ident: ref6/cit6a
  doi: 10.1021/jacs.6b05288
– ident: ref7/cit7b
  doi: 10.1002/anie.201812585
– ident: ref6/cit6e
  doi: 10.1021/ol071080f
– ident: ref12/cit12d
  doi: 10.1021/ja047708o
– ident: ref6/cit6d
  doi: 10.1021/ja063115x
– ident: ref11/cit11g
  doi: 10.1021/acs.orglett.5b00934
– ident: ref11/cit11e
  doi: 10.1055/s-0032-1318145
– volume-title: Chiral Amine Synthesis Methods, Developments and Applications
  year: 2010
  ident: ref3/cit3b
  doi: 10.1002/9783527629541
– ident: ref5/cit5m
  doi: 10.1021/ol902651j
– ident: ref4/cit4a
  doi: 10.1021/jo035245j
– ident: ref8/cit8a
  doi: 10.1002/anie.201607813
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