A Convenient One-Flask Procedure for the Direct Conversion of Alkenes to Homoallylic Alcohols

Schloss, Jeffrey D.; Paquette, Leo A.

doi:10.1080/00397919808004865

Cited by 6 publications

(5 citation statements)

References 6 publications

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“…Ozonides are also known to react directly with organometallic reagents . However, this methodology requires handling of a peroxide intermediate and the use of excess organometallic (to cleave the O–O bond and then react with the liberated carbonyl) …”

Section: Discussionmentioning

confidence: 99%

Tandem Application of C–C Bond-Forming Reactions with Reductive Ozonolysis

Willand‐Charnley

Dussault

2012

J. Org. Chem.

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Several variants of reductive ozonolysis, defined here as the in situ generation of aldehydes or ketones during ozonolytic cleavage of alkenes, are demonstrated to work effectively in tandem with a number of C-C bond-forming reactions. For reactions involving basic nucleophiles (1,2-addition of Grignard reagents, Wittig or Horner-Emmons olefinations, and directed Aldol reactions of lithium enolates) the one-pot process offers a rapid and high-yielding alternative to traditional two-step protocols.

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Section: Discussionmentioning

confidence: 99%

Tandem Application of C–C Bond-Forming Reactions with Reductive Ozonolysis

Willand‐Charnley

Dussault

2012

J. Org. Chem.

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“…Products 1a , 1b , 1c , 1d ,4a 1e , 1f , 1h , 1i , 1j , 1k , 3a , 3c , 3i , 3k , 4c , 5c , 6c , 7c , 8a ,4a 8c , and 8k are all known compounds.…”

Section: Methodsmentioning

confidence: 99%

“…Products 1a, 9 1b, 10 1c, 9 1d, 4a 1e, 11 1f, 12 1h, 9 1i, 9 1j, 9 1k, 9 3a, 9 3c, 9 3i, 9 3k, 9 4c, 13 5c, 9 6c, 14 7c, 15 8a, 4a 8c, 16 and 8k 17…”

Section: Experimental Section Typical Experimental Procedures (Table ...mentioning

confidence: 99%

Direct Preparation of Allylic Indium(III) Reagents from Allylic Alcohols via a Reductive Transmetalation of π-Allylnickel(II) with Indium(I) Iodide

et al. 2004

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InI-mediated direct allylation of carbonyl compounds with allylic alcohols proceeded smoothly with catalytic amounts of Ni(acac)(2) and PPh(3) to give the corresponding homoallylic alcohols in high yields. Allylindium compounds were shown to be the real allylating agents in the present system. Substituted allylic alcohols gave branched homoallylic alcohols with syn-selectivity irrespective of the geometry of the starting allylic alcohols, whereas high anti-selectivity was observed when a bulky substituent is present in the allylic alcohols. The outcome of the diastereoselectivity is discussed on the basis of the reaction mechanism, comparing with the corresponding Pd-catalyzed version. Another distinct behavior between the Ni- and Pd-catalyzed allylation was demonstrated in the reaction of hex-1,5-diene-3,4-diol derivatives: the Pd catalyst did not give any coupling product, whereas the Ni-catalyzed InI-mediated reaction with benzaldehyde afforded the 1:1 and 1:2 adduct diols selectively depending on the reaction conditions.

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“…3,3-Dimethyl-2-phenylpent-4-en-2-ol, 23 (Table 3, Entry 10). 46 Following the general procedure above, 23 was isolated as a yellow oil (0.557 g, 65% yield). 1 H NMR (500 MHz, CDCl 3 ): δ = 1.57 (s, 3H), 2.03 (s, 3H), 5.01 (dd, J = 1.5, 16.5 Hz, 1H), 5.05 (dd, J = 11, 14.0 Hz, 1H), 5.07 (dd, J = 1.5, 9.5 Hz, 1H), 7.41−7.44 (m, 3H), 7.52 (t, J = 9.0 Hz, 1H).…”

mentioning

confidence: 99%

Direct Synthesis of B-Allyl and B-Allenyldiisopinocampheylborane Reagents Using Allyl or Propargyl Halides and Indium Metal Under Barbier-Type Conditions

et al. 2012

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We report the first one-pot process for the asymmetric addition of allyl, methallyl, and propargyl groups to aldehydes and ketones using B-chlorodiisopinocampheylborane ((d)DIP-Cl) and indium metal. Under Barbier-type conditions, indium metal was used to generate allyl- and allenylindium intermediates, and subsequent reaction with (d)DIP-Cl successfully promoted the transfer of these groups to boron forming the corresponding chiral borane reagents. The newly formed borane reagents were reacted with aldehydes and ketones to produce the corresponding alcohol products in high yields and up to excellent enantioselectivity (98% ee). This method produced excellent enantioenriched secondary homoallylic alcohols from the allylation and methallylation of benzaldehyde. Using this method, the methallylation and cinnamylation of ketones afforded the highest enantioselectivities, while the propargylation of both aldehydes and ketones provided low enantiomeric excesses. In addition, this procedure provided the first synthesis of B-allenyldiisopinocampheylborane, which was characterized by (1)H and (11)B NMR spectroscopy. This is the first example of the direct synthesis of allylboranes that contained substitutions from the corresponding allyl bromide and indium, thereby expanding the utility of the DIP-Cl reagent. Hence, a general and straightforward route to these chiral organoborane reagents in one-pot has been developed along with the asymmetric Barbier-type allylation and propargylation of aldehyde and ketone substrates using these chiral organoborane reagents in subsequent coupling reactions.

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A Convenient One-Flask Procedure for the Direct Conversion of Alkenes to Homoallylic Alcohols

Cited by 6 publications

References 6 publications

Tandem Application of C–C Bond-Forming Reactions with Reductive Ozonolysis

Tandem Application of C–C Bond-Forming Reactions with Reductive Ozonolysis

Direct Preparation of Allylic Indium(III) Reagents from Allylic Alcohols via a Reductive Transmetalation of π-Allylnickel(II) with Indium(I) Iodide

Direct Synthesis of B-Allyl and B-Allenyldiisopinocampheylborane Reagents Using Allyl or Propargyl Halides and Indium Metal Under Barbier-Type Conditions

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