Borane and alane reductions of bulky N,N′-diaryl-1,3-diimines: Structural characterization of products and intermediates in the diastereoselective synthesis of 1,3-diamines

David T. Carey; Francis S. Mair; Robin G. Pritchard; John E. Warren; Rebecca J. Woods

doi:10.1039/b306401h

Borane and alane reductions of bulky N,N′-diaryl-1,3-diimines: Structural characterization of products and intermediates in the diastereoselective synthesis of 1,3-diamines

David T. Carey, Francis S. Mair, Robin G. Pritchard, John E. Warren, Rebecca J. Woods

Research output: Contribution to journal › Article › peer-review

Abstract

Two new C2-symmetric diazaborinanes were prepared by diastereoselective intramolecular dihydroboration of bulky 1,3-diamines, the remarkably stable l-[HB(2,6-Pr2i-C6H3 NCHMe)2CMe2], from which it was not possible to isolate free diimine, and the less bulky l-[HB(2-Pri-C6 H4NCHMe)2CMe2], which yielded l-(2-Pri-C6H4NHCHMe)2 CMe2 on acid work up. The BH3 reductions were highly diastereoselective for l-products (de > 95%). Use of AlCl3/LiAlH4 mixtures in diethyl ether gave lower (de ≈ 75%) and opposite selectivity, yielding predominantly u-(2,6-Pr2i - C6H3NHCHMe)2CMe2 upon work up, via a u-[H2Al(2,6-Pr2i- C6H3)NHCHMeCMe2CHMeN(2,6- Pr2i-C6H3)] intermediate in a two-step reduction. All products were characterized crystallographically.

Original language	English
Pages (from-to)	3792-3798
Number of pages	6
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	19
DOIs	https://doi.org/10.1039/b306401h
Publication status	Published - 7 Oct 2003

Keywords

BETA-DIIMINE
{BETA-DIIMINE
{BOND
BORON-NITROGEN
BORON-NITROGEN} {BOND
CHEMISTRY
{CHEMISTRY
LIGANDS
complexes
{COMPLEXES
crystal
crystal structure
{CRYSTAL} {STRUCTURE
COMPLEXES
DERIVATIVES
REACTIVITY
{DERIVATIVES
MOLECULAR-STRUCTURE
{MOLECULAR-STRUCTURE
{REACTIVITY
SOLID-STATE
SOLID-STATE} {STRUCTURE
{SOLID-STATE} {STRUCTURE
BORON-NITROGEN BOND
{STRUCTURE

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10.1039/b306401h

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@article{c924e9f4ccbc4c14856768bb62150254,

title = "Borane and alane reductions of bulky N,N′-diaryl-1,3-diimines: Structural characterization of products and intermediates in the diastereoselective synthesis of 1,3-diamines",

abstract = "Two new C2-symmetric diazaborinanes were prepared by diastereoselective intramolecular dihydroboration of bulky 1,3-diamines, the remarkably stable l-[HB(2,6-Pr2i-C6H3 NCHMe)2CMe2], from which it was not possible to isolate free diimine, and the less bulky l-[HB(2-Pri-C6 H4NCHMe)2CMe2], which yielded l-(2-Pri-C6H4NHCHMe)2 CMe2 on acid work up. The BH3 reductions were highly diastereoselective for l-products (de > 95\%). Use of AlCl3/LiAlH4 mixtures in diethyl ether gave lower (de ≈ 75\%) and opposite selectivity, yielding predominantly u-(2,6-Pr2i - C6H3NHCHMe)2CMe2 upon work up, via a u-[H2Al(2,6-Pr2i- C6H3)NHCHMeCMe2CHMeN(2,6- Pr2i-C6H3)] intermediate in a two-step reduction. All products were characterized crystallographically.",

keywords = "BETA-DIIMINE, \{BETA-DIIMINE, \{BOND, BORON-NITROGEN, BORON-NITROGEN\} \{BOND, CHEMISTRY, \{CHEMISTRY, LIGANDS, complexes, \{COMPLEXES, crystal, crystal structure, \{CRYSTAL\} \{STRUCTURE, COMPLEXES, DERIVATIVES, REACTIVITY, \{DERIVATIVES, MOLECULAR-STRUCTURE, \{MOLECULAR-STRUCTURE, \{REACTIVITY, SOLID-STATE, SOLID-STATE\} \{STRUCTURE, \{SOLID-STATE\} \{STRUCTURE, BORON-NITROGEN BOND, \{STRUCTURE",

author = "Carey, \{David T.\} and Mair, \{Francis S.\} and Pritchard, \{Robin G.\} and Warren, \{John E.\} and Woods, \{Rebecca J.\}",

year = "2003",

month = oct,

day = "7",

doi = "10.1039/b306401h",

language = "English",

pages = "3792--3798",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

number = "19",

}

Borane and alane reductions of bulky N,N′-diaryl-1,3-diimines: Structural characterization of products and intermediates in the diastereoselective synthesis of 1,3-diamines. / Carey, David T.; Mair, Francis S.; Pritchard, Robin G. et al.
In: Journal of the Chemical Society, Dalton Transactions, No. 19, 07.10.2003, p. 3792-3798.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Borane and alane reductions of bulky N,N′-diaryl-1,3-diimines: Structural characterization of products and intermediates in the diastereoselective synthesis of 1,3-diamines

AU - Carey, David T.

AU - Mair, Francis S.

AU - Pritchard, Robin G.

AU - Warren, John E.

AU - Woods, Rebecca J.

PY - 2003/10/7

Y1 - 2003/10/7

N2 - Two new C2-symmetric diazaborinanes were prepared by diastereoselective intramolecular dihydroboration of bulky 1,3-diamines, the remarkably stable l-[HB(2,6-Pr2i-C6H3 NCHMe)2CMe2], from which it was not possible to isolate free diimine, and the less bulky l-[HB(2-Pri-C6 H4NCHMe)2CMe2], which yielded l-(2-Pri-C6H4NHCHMe)2 CMe2 on acid work up. The BH3 reductions were highly diastereoselective for l-products (de > 95%). Use of AlCl3/LiAlH4 mixtures in diethyl ether gave lower (de ≈ 75%) and opposite selectivity, yielding predominantly u-(2,6-Pr2i - C6H3NHCHMe)2CMe2 upon work up, via a u-[H2Al(2,6-Pr2i- C6H3)NHCHMeCMe2CHMeN(2,6- Pr2i-C6H3)] intermediate in a two-step reduction. All products were characterized crystallographically.

AB - Two new C2-symmetric diazaborinanes were prepared by diastereoselective intramolecular dihydroboration of bulky 1,3-diamines, the remarkably stable l-[HB(2,6-Pr2i-C6H3 NCHMe)2CMe2], from which it was not possible to isolate free diimine, and the less bulky l-[HB(2-Pri-C6 H4NCHMe)2CMe2], which yielded l-(2-Pri-C6H4NHCHMe)2 CMe2 on acid work up. The BH3 reductions were highly diastereoselective for l-products (de > 95%). Use of AlCl3/LiAlH4 mixtures in diethyl ether gave lower (de ≈ 75%) and opposite selectivity, yielding predominantly u-(2,6-Pr2i - C6H3NHCHMe)2CMe2 upon work up, via a u-[H2Al(2,6-Pr2i- C6H3)NHCHMeCMe2CHMeN(2,6- Pr2i-C6H3)] intermediate in a two-step reduction. All products were characterized crystallographically.

KW - BETA-DIIMINE

KW - {BETA-DIIMINE

KW - {BOND

KW - BORON-NITROGEN

KW - BORON-NITROGEN} {BOND

KW - CHEMISTRY

KW - {CHEMISTRY

KW - LIGANDS

KW - complexes

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KW - crystal

KW - crystal structure

KW - {CRYSTAL} {STRUCTURE

KW - COMPLEXES

KW - DERIVATIVES

KW - REACTIVITY

KW - {DERIVATIVES

KW - MOLECULAR-STRUCTURE

KW - {MOLECULAR-STRUCTURE

KW - {REACTIVITY

KW - SOLID-STATE

KW - SOLID-STATE} {STRUCTURE

KW - {SOLID-STATE} {STRUCTURE

KW - BORON-NITROGEN BOND

KW - {STRUCTURE

UR - https://www.scopus.com/pages/publications/0142165740

U2 - 10.1039/b306401h

DO - 10.1039/b306401h

M3 - Article

SN - 1472-7773

SP - 3792

EP - 3798

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 19

ER -

Borane and alane reductions of bulky N,N′-diaryl-1,3-diimines: Structural characterization of products and intermediates in the diastereoselective synthesis of 1,3-diamines

Abstract

Keywords

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CCDC 212235: Experimental Crystal Structure Determination

CCDC 212233: Experimental Crystal Structure Determination

CCDC 212232: Experimental Crystal Structure Determination

Cite this

Borane and alane reductions of bulky N,N′-diaryl-1,3-diimines: Structural characterization of products and intermediates in the diastereoselective synthesis of 1,3-diamines

Abstract

Keywords

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Datasets

CCDC 212235: Experimental Crystal Structure Determination

CCDC 212233: Experimental Crystal Structure Determination

CCDC 212232: Experimental Crystal Structure Determination

Cite this