2003 Fiscal Year Final Research Report Summary
A novel preparation of allylic tins applying the reduction of tin(IV) chloride with iodide and its application
| Project/Area Number |
14540549
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
物質変換
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| Research Institution | Sophia University |
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Principal Investigator |
MASUYAMA Yoshiro Sophia University, Faculty of Science and Technology, Lecturer, 理工学部, 講師 (30138375)
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| Project Period (FY) |
2002 – 2003
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| Keywords | carbonyl-allylation / allyltrihalotin / tin(IV) chloride / tin(IV) iodide / tetrabutylammonium iodide / sodium iodide / nucleophilic addition / diastereoselectivity |
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| Research Abstract |
Tin(IV) halides were reduced to trihalostannates(II) with iodide in dichloromethane via the formation of pentahalostannates(IV). The trihalostannates(II) reacted with allylic chlorides or allylic mesylates to prepare allyltrihalotins, which caused nucleophilic addition to aldehydes to afford the corresponding homoallylic alcohols. The trihalostannates(II) were applied into the preparation of propargyltrihalotins and allenyltrihalotins. (1)Carbonyl allylation: 2-Propenyltrichlorotin, derived from 3-chioropropene or 2-propenyl mesylate with tin(IV) chloride and three equimolar amount of tetrabutylammonium iodide (TBAI), caused nucleophilic addition to aldehydes to afford the corresponding homoallylic alcohols in high yields. The carbonyl allylation with 1-chloro-2-butene remained in low yields. The use of tin(IV) iodide instead of tin(IV) chloride cut down the amount of TBAI (two equimolar amount) and enhanced the yields of carbonyl allylation with 1-chloro-2-butene. Sodium iodide instead of TBAI was utilized in 1,3-imidazolidin-2-one. (2)Carbonyl allenylation and propargylation: Carbonyl allenylation and propargylation were carried out with 2-propynyl chloride or mesylate similarly to the carbonyl allylation mentioned above. The reaction of 1-methyl-2-propynyl mesylate or 2-butynyl mesylate with aldehydes afforded the corresponding 2-methyl-3-butyn-1 -ols or 2-methyl-2,3-butadien-1-ols respectively.
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