AN UNEXPECTED 1,2-ALKYL SHIFT WITHIN A CHELATE BONDED ORGANOALUMINUM-ENAMINE

被引：23

作者：

WISSING, E ^{[1
]}

JASTRZEBSKI, JTBH ^{[1
]}

BOERSMA, J ^{[1
]}

VANKOTEN, G ^{[1
]}

机构：

[1] UNIV UTRECHT,DEBYE INST,DEPT MET MEDIATED SYNTHESIS,PADUALAAN 8,3584 CH UTRECHT,NETHERLANDS

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1993年 / 459卷 / 1-2期

关键词：

D O I：

10.1016/0022-328X(93)86050-R

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The organozinc-enamines EtZn[R'N-CH=CH-N(Et)R'] (R=(t)Bu (1a), (t)pent (2a), (i)Pr (3a)) react with Et3Al via a transmetallation reaction to the corresponding organoaluminium-enamines Et2Al[R'N-CH=CH-N(Et)R'] (R'=(t)Bu (1c), (t)pent (2c)) and Et2Zn. Prior to the transmetallation reaction initial 1 : 1 zinc-enamine-trialkylaluminium adducts are formed. Compounds 1c and 2c are thermally unstable and rearrange via a 1,2-alkyl shift partly in combination with a hydrogen shift, to Et2Al[R'N=CH-C(H)R'-NEt] (R'=(t)Bu (1d), (t)pent (2d)) (70%) and Et2Al[R'N-CH2CR'=NEt] (R'=(t)Bu (1e), (t)pent (2e)) (30%). The driving force for the alkyl shift, which is restricted to tertiary alkyl groups, is release of steric strain in the five-membered NCCN aluminium chelate ring.

引用

页码：11 / 16

页数：6

共 50 条

[1] SYNTHESIS OF 2-ALKYL AND 1,2-DIALKYLPROPANESULTAMS
KOBAYASHI, M
OKAHARA, M
KOMORI, S
AGAWA, T
[J]. SYNTHESIS-STUTTGART, 1973, (11): : 667 - 669
[2] C-H Functionalization of Heterocycles with Triplet Carbenes by means of an Unexpected 1,2-Alkyl Radical Migration
Empel, Claire
Jana, Sripati
Ciszewski, Lukasz W.
Zawada, Katarzyna
Pei, Chao
Gryko, Dorota
Koenigs, Rene M.
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2023, 29 (29)
[3] Lewis acid-catalyzed 1,2-alkyl shift in allenyl ketones: Synthesis of multisubstituted furans
Dudnik, Alexandr S.
Gevorgyan, Vladimir
[J]. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2007, 233
[4] Electrochemical Oxidative Arylsulfonylation and 1,2-Alkyl Shift Sequences of Alkenyl Cyclobutanols for the Synthesis of β-Sulfonated Cyclopentanones
Kim, Yebin
Kim, Dae Young
[J]. BULLETIN OF THE KOREAN CHEMICAL SOCIETY, 2021, 42 (03) : 510 - 513
[5] ION-MOLECULE COMPLEXES IN 1,2-ALKYL SHIFTS
GAPPA, A
HERPERS, E
HERRMANN, R
HULSEWEDE, V
KAPPERT, W
KLAR, M
KIRMSE, W
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (49) : 12096 - 12106
[6] Gold-catalyzed intermolecular reaction of ynamides with 3-indolyl azides via an unexpected 1,2-alkyl migration
Bo Zhou
Ying-Qi Zhang
Xin Liu
Long-Wu Ye
[J]. Science Bulletin, 2017, 62 (17) : 1201 - 1206
[7] Gold-catalyzed intermolecular reaction of ynamides with 3-indolyl azides via an unexpected 1,2-alkyl migration
Zhou, Bo
Zhang, Ying-Qi
Liu, Xin
Ye, Long-Wu
[J]. SCIENCE BULLETIN, 2017, 62 (17) : 1201 - 1206
[8] ORGANOMETALLOIDAL DERIVATIVES OF THE TRANSITION-METALS .5. A 1,2-ALKYL SHIFT FROM LEAD TO A TRANSITION-METAL
PANNELL, KH
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1980, 198 (01) : 37 - 40
[9] 1,2-ALKYL SHIFT, FROM CARBON TO POSITIVE NITROGEN, IN SIMPLE, OPEN-CHAIN N,N-DICHLOROALKYLAMINES
KLING, TA
NAZARENO, MB
KOVACIC, P
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (06) : 2157 - &
[10] Photochemistry of aryloxiranes: free radical 1,2-alkyl migrations in a constrained system
Arney, BE
White, RC
Ramanathan, A
Barham, L
Sherrod, S
McCall, P
Livanec, P
Mangus, K
White, K
[J]. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, 2004, 3 (09) : 851 - 853

← 1 2 3 4 5 →